applied
sciences
Review
The Technology of Tail Gases Purifying in Nitric Acid Plants
and Design of deN2O and deNOx Reactors—Review
Paweł Capała 1, * , Monika Ruszak 1 , Anna Rudawska 2 , Marek Inger 1
Citation: Capała, P.; Ruszak, M.;
Rudawska, A.; Inger, M.; Wilk, M.
The Technology of Tail Gases
Purifying in Nitric Acid Plants and
Design of deN2 O and deNOx
Reactors—Review. Appl. Sci. 2023, 13,
7492. https://doi.org/10.3390/
app13137492
Academic Editor: Weifeng Li
Received: 27 April 2023
Revised: 15 June 2023
Accepted: 21 June 2023
Published: 25 June 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Appl. Sci. 2023, 13, 7492. https://doi.org/10.3390/app13137492
and Marcin Wilk 1
1 Łukasiewicz Research Network—New Chemical Syntheses Institute, Al. Tysiaclecia
˛ Państwa Polskiego 13a,
24-110 Puławy, Poland; monika.ruszak@ins.lukasiewicz.gov.pl (M.R.);
marek.inger@ins.lukasiewicz.gov.pl (M.I.); marcin.wilk@ins.lukasiewicz.gov.pl (M.W.)
2 Faculty of Mechanical Engineering, Lublin University of Technology, Nadbystrzycka 36 St,
20-618 Lublin, Poland; a.rudawska@pollub.pl
* Correspondence: pawel.capala@ins.lukasiewicz.pl; Tel.: +48-814731466
Abstract: The tightening standards of nitrogen oxides emission from industrial plants encourage
nitric acid producers to search for new efficient solutions to meet the stringent emission limits.
Industrial practice and the patent literature show that the effectiveness of deNOx (SCR) and deN2 O
technology is affected not only by the type and shape of the catalyst, but also by the method of its
installation in a heterogenous catalytic reactor. The article presents the background of the problem,
related to the emission of nitrogen oxides from nitric acid plants, and describes the technology
of the tail gases purified from NOx and N2 O. It shows various aspects that should be considered
in designing reactors for deNOx and deN2 O processes in nitric acid plants. The advantages and
disadvantages of different catalytic basket designs, their industrial application and the direction of
their design development were also indicated.
Keywords: heterogenous catalytic reactor; catalytic basket design; nitric acid plants; tail gases
purifying; deNOx technology; deN2 O technology
1. Introduction
The continuous development of technologies for removing harmful components
of industrial off-gasses is a consequence of increasingly stringent emission standards
and society’s growing awareness about the need to protect the environment for future
generations. The term “hazardous gases” refers to substances harmful to human health,
the environment and construction materials. In the case of nitric acid plants, these gases
are nitrogen oxides, N2 O and NOx (NO, NO2 ).
Nitrous oxide (N2 O) is non-toxic to living organisms, but it is a greenhouse gas with
a GWP index (Global Warming Potential) 265–300 times greater than CO2 [1]. Due to the
high efficiency in absorbing infrared radiation, reducing its emission, even to a small extent,
results in a significant reduction in CO2 equivalent emission. Accumulation of N2 O is
favoured by its long lifetime in the atmosphere, estimated at 116 years [2]. Nitrous oxide
also indirectly contributes to the destruction of the ozone layer in the stratosphere, where it
is photolyzed and reacts with oxygen to NOx , which reacts then with O3 [2,3].
In nitric acid plants, nitrous oxide (N2 O) is formed as a by-product in the process
of ammonia oxidation to NO, carried out in the presence of Pt-Rh-Pd catalytic gauzes
package [4]:
2NH3 + 2O2 ® N2 O + 3H2 O + 736 kJ/mol (1)
Moreover, it can also be formed downstream of the catalytic gauzes package in the
reaction of unreacted ammonia with NO (Equation (2)), as well as in the process of selective
https://www.mdpi.com/journal/applsci
Appl. Sci. 2023, 13, 7492 2 of 27

catalytic reduction of NOx (deNOx ), carried out in SCR reactors, installed downstream of
the absorption column (Equations (1) and (3)):

2NH3 + 8NO → 5N2 O + 3H2 O + 945.7 kJ (2)

4NO + 4NH3 + 3O2 → 4N2 O + 6H2 O + 2403.3 kJ (3)

Nitrous oxide is chemically inert and stable at temperatures <700 ◦ C. Therefore,
without using technology for its removal, it does not undergo any changes in the entire
technological line of nitric acid production and is emitted into the atmosphere with the
tail gases stream at a concentration of 500–2000 ppm (depending on the plant type). The
nitrous oxide emission can reach a level of ~5 kg/t HNO3 , ~7 kg/t HNO3 and ~12 kg/t
HNO3 for low-, medium- and high-pressure plants, respectively [5].
Nitrogen oxides, referred to as NOx , are not classified as greenhouse gases, although
they are included in the overall radiation balance [6]. Unlike N2 O, they have a significant
harmful effect on human health. They cause respiratory and cardiovascular diseases, and
sometimes cancer or even death. They also harm the environment, contributing to the
formation of acid rain and the destruction of the ozone layer in the stratosphere. In addition,
they react with other air pollutants, creating the so-called photochemical smog [7,8].
Nitric oxide (NO) is the main product formed in the process of ammonia oxidation,
carried out in the presence of Pt-Rh-Pd catalytic gauzes package [4]:

4NH3 + 5O2 → 4NO + 6H2 O + 904 kJ/mol (4)

In the technological line of the plant between the ammonia burner and the absorption
column, NO partially oxidizes to NO2 :

2NO +O2 ↔ 2NO2 (5)

In this area of the plant, the presence of NO and NO2 in the gas stream (so-called
nitrous gases) is desirable for the production of nitric acid:

3NO2 + H2 O → 2HNO3 + NO (6)

Reaction (6) occurs in the liquid phase on the sieve trays (plates) of the absorption
column. Additionally, reaction (5) occurs inside the column between the plates in the gas
phase. The efficiency of nitrogen oxides absorption in water is never 100%. Therefore,
NO and NO2 are always present in the so-called tail gases stream, leaving the absorption
column. In this area of the nitric acid plant, they are treated as pollutants. Their amount
depends on the size of the absorption column and the conditions in which the absorption
process is carried out, i.e., temperature, pressure and gas flow rate. The content of nitrogen
oxides in the tail gases stream is usually 2–3 wt. % in relation to the amount of nitric acid
produced. Thus, without the technology of NOx removal, their concentration downstream
of the absorption column may reach even 3000 ppm for low-pressure plants [4,9–11].
NOx and N2 O emissions are regulated by the Directive of the European Parliament on
industrial emissions 2010/75/EU. Under the guidelines contained in the Official Journal
of the European Union L248/3 [12] and the BAT document (Best Available Techniques
Reference Document) [13], the current emission limits are 300 ppm N2 O and 90 ppm
NOx for the existing nitric acid plants, while 100 ppm N2 O and 75 ppm NOx for the new
ones [9]. Due to the European Union’s pursuit of a “zero-emission” economy, these limits
are expected to be tightened in the future. There are two aspects in favour of reducing
N2 O emissions: environmental and economic. According to the “European Green Deal”
communication presented by the European Commission in 2019, by 2030, CO2 equivalent
emissions from industrial plants should be reduced by at least 42% in the so-called non-ETS
countries (the current level is 30%) and by at least 52% in the EU-ETS countries (the current
level is 43%), in relation to the emissions recorded in 2005. This involves the need to reduce
Appl. Sci. 2023, 13, 7492 3 of 27

greenhouse gas emissions, even in the plants that have been considered low-emission. The
second aspect in favour of lowering N2 O emission is related to the possibility of CO2 eq
emission allowances trading. Currently, the reduction in nitrous oxide emissions to a level
lower than that resulting from the established emission standards gives a profit of several
dozen EUR/day for each additional 1 ppm of N2 O reduced [14–16].
Due to the tightening legal requirements regarding N2 O and NOx emission standards
and the economic aspect, scientists and engineers put much effort into improving the tech-
nology for removing these harmful gaseous pollutants from nitric acid plants. Most of the
work is focused on developing and testing the catalysts for N2 O decomposition/reduction
(deN2 O) and NOx reduction. Only a few scientific and technical studies concern the design
of catalytic baskets or reactors for the deNOx /deN2 O processes (Section 2). The indus-
trial experience of Łukasiewicz-INS shows that the design and technical condition of the
catalytic basket, supporting a catalyst bed, significantly influences the catalyst efficiency.
The article presents solutions in the field of technology for removing N2 O and NOx
from the tail gases in nitric acid plants, focusing mainly on the design of the catalytic
baskets, installed inside deNOx /deN2 O reactors.

2. Technologies for Purifying the Tail Gases from N2 O and NOx

According to the BAT guidelines [13], the best available technologies for nitrous oxide
emission abatement in nitric acid plants are a high-temperature catalytic N2 O decomposi-
tion in the nitrous gases stream (HT-deN2 O), low-temperature decomposition (LT-deN2 O)
and catalytic reduction of N2 O in the tail gases stream. The first of these processes is
carried out in an ammonia oxidation reactor, where achieving a profound reduction in
N2 O emissions, exceeding 95% of the initial value, is technologically very difficult. A low-
temperature N2 O decomposition or reduction technology is a more practical and effective
solution. The implementation of the N2 O removal process at the end of the technological
line of nitric acid production (downstream of the absorption column) for a given type
of catalyst allows for achieving a nearly 100% reduction in N2 O emission, by selecting
the appropriate catalyst load, as well as the design of the catalytic basket and deN2 O
reactor [17].
The process of catalytic N2 O reduction is mainly carried out in the presence of zeolites
(e.g., ZSM-5, BEA, MFI, FAU or FER) modified with iron or copper ions (in the presence of
Fe-FER a simultaneous reduction of NOx and N2 O is possible) [18]. Hydrogen, or more
often hydrocarbons (e.g., methane, propane), are used as a reducing agent:

CH4 + 4N2 O → CO2 + 2H2 O + 4N2 (T = 350–450 ◦ C) (7)

N2 O reduction with ammonia is also possible in the presence of iron-modified zeolites.

However, this process is non-selective in the presence of NOx and requires an operating
temperature >440 ◦ C to achieve 95% N2 O reduction [17,19,20].
In a low-temperature catalytic N2 O decomposition process, catalysts based on tran-
sition metals (Cu, Co, Fe, Ni) on various supports, i.e., ZnO, CeO2 , Al2 O3 , TiO2 , ZrO2 ,
hydrotalcite, perovskite and zeolite, can be used. Among the transition metal oxides,
spinel-based catalysts, e.g., Fe3 O4 and Co3 O4 are preferred. A particular difficulty in using
catalysts based on transition metal oxides may be the inhibitory effect of other tail gases
components (i.e., NOx , O2 or H2 O) on the deN2 O process. Purifying the tail gases at a
temperature >350 ◦ C can reduce the adverse effect of the water presence on the activity
of these spinels. The problem with NOx influence can be solved by using a reactor with a
deNOx /deN2 O dual-bed catalytic system, in which the gas stream is first purified of NOx .
In the process of low-temperature N2 O decomposition, zeolite catalysts modified with
copper and iron ions are also used, the most popular of which is Fe-ZSM-5. These catalysts
can perform a dual function of catalyzing the N2 O decomposition and NOx reduction.
A commercial catalyst for N2 O decomposition is, for example, Clariant EnviCat®N2 O in
the form of trillobes, ensuring over 99% efficiency of N2 O removal from the tail gases
stream [21–25].
Appl. Sci. 2023, 13, 7492 4 of 27

One of the best available techniques for reducing NOx emissions from nitric acid
plants is the selective catalytic reduction of NOx with ammonia, carried out between the
absorption column and the expansion turbine. Such a location enables the deNOx process
to be carried out under high pressure, which allows for using a smaller volume of the
catalyst bed than installing the reactor downstream of the expansion turbine. In such cases,
preheating the tail gases to the operating temperature of the catalyst is often not required.
However, in the case of tail gases purifying upstream of the expansion turbine, apart from
the operating temperature, selecting a suitable form of the catalyst is also crucial. It should
ensure low-pressure drops across the catalyst bed, not causing significant energy losses at
the gas inlet of the expansion turbine [13,26,27].
The selective catalytic reduction of NOx with ammonia, depending on the temperature,
oxygen content and NO2 /NOx molar ratio in the purified tail gases, can proceed according
to the following reactions:

4NO + 4NH3 + O2 → 4N2 + 6H2 O (8)

NO + NO2 + 2NH3 → 2N2 + 3H2 O (9)

2NO2 + 4NH3 + O2 → 3N2 + 6H2 O (10)

Under non-optimal process conditions for a given type of catalyst, undesirable side
reactions may occur in the reactor, leading to the formation of N2 O and NO [28–31]. The
selective catalytic reduction of NOx with ammonia is usually carried out at a temperature
higher than 200 ◦ C, due to the risk of ammonium nitrate accumulation in the reactor.
The upper limit of the process temperature is determined by the type of catalyst and the
maximum operating temperature of the expansion turbine [32]. In the case of oxide catalysts
based on transition metals (e.g., V2 O5 ), it should be equal to or lower than 400 ◦ C, because
at higher temperatures the share of undesirable side reactions of ammonia oxidation to N2 O
and NO in the deNOx process increases [33]. In the case of some zeolites modified with
iron ions, it is possible to conduct the deNOx process at temperatures up to 600 ◦ C [34,35].
Moreover, for this type of catalyst, using a temperature >400 ◦ C is beneficial due to the
increase in their activity in N2 O reduction with ammonia (e.g., in the presence of Fe-ZSM-5
zeolite) [17,36,37].
Based on the scientific and patent literature, it can be concluded that the preferred
catalysts for the deNOx process are: oxides of transition metals [38–41], rare earth met-
als [42] and zeolites modified with transition metals ions [31,43–46]. In the case of metal
oxides, they are often deposited on ceramic supports, i.e., TiO2 , Al2 O3 , SiO2 , ZrO2 and
CeO2 , which increase the mechanical strength of the catalyst and the stability of its oper-
ation. Commercial catalysts used in nitric acid plants in the deNOx process are mainly
V2 O5 supported on Al2 O3 [47] or TiO2 [29,30,33,48] and high-silicon zeolites (MFI, BEA,
FER, MOR, FAU, MEL, SAPO-18/SAPO-34 and most often ZSM-5) [49–51] modified with
transition metal ions, i.e., Cu (Cu-CHA [31,52], Cu-ZSM-34 [44]) and Fe (e.g., Fe-BEA [34],
Fe-ZSM-5 [35,43]).
Some of the literature and patent studies focus on methods of NOx removal from the
tail gases stream in a two-stage process, combined with N2 O removal. These are mainly
different variants of EnviNOx (Tyssen Krupp/UHDE) process, consisting of:
• Variant I—catalytic decomposition of N2 O and selective catalytic reduction of NOx
with ammonia in the tail gases stream, which is used in the plants with the tail gases
temperature in the range of 425–520 ◦ C [27,43,53,54]:
2N2 O → 2N2 + O2 (11)

6NO2 + 8NH3 → 7N2 + 12 H2 O (12)

4NO + O2 + 4NH3 → 4N2 + 6H2 O (13)

Appl. Sci. 2023, 13, 7492 5 of 27

• Variant II—selective catalytic reduction of NOx with ammonia (reactions 12 and

13) and selective catalytic reduction of N2 O with hydrocarbons (reaction 14, e.g.,
methane) in the tail gases stream, most commonly used in the plants with the tail gases
temperature <425 ◦ C (guaranteed operating temperature range 340–520 ◦ C) [27,53,54]:

(3n + 1) N2 O + Cn H2n+2 → (3n + 1) N2 + n CO2 + (n + 1) H2 O (14)

The EnviNOx technology allows N2 O removal with 98–99% efficiency and for re-
ducing NOx emission to <10 ppm. Above 45 EnviNOx units operate in nitric acid plants
worldwide [55]. The temperature range in which the tail gases purifying from nitrogen
oxides is carried out is 300–650 ◦ C.
Casale S. A. additionally proposed a solution consisting of three-stage purifying of
the tail gases from NOx and N2 O. NOx is reduced with ammonia on a first and third
bed of a zeolite catalyst modified with iron or copper ions. On the second bed of iron-
modified zeolite catalyst, N2 O is removed via a catalytic decomposition. The efficiency of
this solution in purifying the tail gases from NOx is above 95% [56].
The efficiency of the SCR process is verified based on the maximum NOx and N2 O
conversion (reduction or decomposition), that can be achieved on the catalyst bed, and
ammonia slip (translating into ammonia consumption index). The conversion degree is
determined by measuring the concentration of NOx and N2 O at the reactor inlet and outlet
during the tail gases’ purifying process. In addition, the pressure drop across the catalyst
bed is also measured, especially in the case of high-pressure plants. Its value translates into
the amount of energy recovery in the expansion turbine.
The main parameters that affect the catalyst efficiency in the deNOx (SCR) reactor
are GHSV (Gas Hourly Space Velocity), NH3 /NOx molar ratio and operating temperature.
GHSV determines the residence time of the tail gases components in the reaction zone
(expressed as the ratio of the gas flow rate and the catalyst bed volume). The value of this
parameter increases with the increase in the tail gases flow rate, which may translate into a
reduction in the nitrogen oxides conversion on a given catalyst bed. For the plants with
high gas flow rates, the deNOx and deN2 O process efficiency can be improved by lowering
the linear gas velocity, using a catalytic basket of appropriate design. In the deNOx
process, controlling the NH3 /NOx molar ratio is necessary to minimize NH3 slip and
reduce the ammonia consumption index while maintaining a high NOx conversion. At the
operating temperature lower than the optimum for a given catalyst type, the concentration
of a reducing agent in the tail gases stream has little effect on the NOx reduction. It
may contribute to the increase in ammonia slip. The efficiency of the deNOx process
increases with increasing NH3 /NOx molar ratio at the temperatures close to the optimum
temperature for a given catalyst. Above this temperature, a decrease in the NOx reduction
rate is observed, despite the increase in the NH3 /NOx molar ratio. This is due to the
increased share of undesirable side reactions (e.g., ammonia oxidation to N2 O). Therefore,
for each catalyst, the temperature window for the deNOx process is defined, i.e., the
temperature range of its optimal operation [7,33,57,58].
The deNOx or deN2 O catalysts can be formed in various shapes, i.e., extrudates,
trillobes, spheres, stars, monoliths, foams or metal wire gauzes, which affect the design of
the reactor interior. The shape of the catalyst determines the size of its geometric surface
area available for the reactants, and the gas pressure drops across the catalyst bed. Higher
gas flow resistances are caused by the catalyst beds in the form of grains, while the lowest
are caused by the catalysts in the form of monoliths or gauzes. High-pressure drops and
diffusion resistances characterize packed bed reactors, while these resistances are more
significant the smaller the shaped catalyst body forming the bed. Monolithic catalysts
usually have the form of honeycomb blocks. They are typically made of ceramic (cordierite)
or metallic material (stainless steel, metal alloys), coated with the active phase of the catalyst.
Bulk catalysts can also be shaped this way (without using support). Monolithic catalysts
are characterized by a high specific surface area, low thermal expansion and high thermal
shock resistance. Their manufacturing process is easy to scale up. Their disadvantages
Appl. Sci. 2023, 13, 7492 6 of 27

are the lack of reactants radial mixing, low rates of interfacial mass and heat exchange. In
addition to the solid catalyst blocks, monoliths can also have a foam structure, made of
metal or ceramics. They are characterized by a high surface area-to-volume ratio. Their
advantages are low pressure drop across the catalyst bed (however higher than in the case
of standard monoliths), high mass and heat transfer coefficients, good radial mixing, higher
gas flow disturbances in the material’s tortuous channels, high specific surface area and
porosity. Heat transfer occurs in three ways: via convection, radiation and conduction.
Catalysts in the form of gauzes, made of metals or steel coated with an active phase (e.g.,
FeCeW catalysts supported on SSWM gauzes), are characterized by: high rates of mass
and heat transfer and low pressure drops. In this case, the internal and external diffusion
resistances and pressure drop are greatly influenced by the supports’ structure. For the
catalyst in the form of gauzes, the limitations related to the external diffusion resistances
are eliminated (pore and axial diffusion), and a reactor with a dimension up to 10 times
smaller than the reactor with a monolithic catalyst can be used. They can be used in nitric
acid plants with high tail gases flow rates. The structure of such a catalyst is flexible, so
its efficiency can be easily influenced by changing the size and shape of the gauzes, wire
diameter or gauzes packing density. Fluidized bed reactors provide the best gas–solid body
contact; therefore, their dimensions can be smaller than those of packed or monolythic bed
reactors. However, this requires using catalysts with high mechanical strength, because
during fluidization, abrasion of the catalyst bed may occur [37,59,60].
The pressure drop value is affected by the form and size of the shaped catalyst body
and the linear gas flow velocity through the catalyst bed. The latter depends on the method
of the catalyst bed installation inside the reactor. Figure 1 shows an exemplary dependence
of the gas pressure drops on the linear gas flow velocity in the radial reactor, for the catalysts
in the form of 3 mm diameter extrudates and 8 mm diameter tablets. It was determined
based on deNOx tests in the SCR reactor in a pilot nitric acid plant. The parameters of the
catalyst bed were as follows: bed dimensions s × h = 0.058 m2 × 0.39 m (s—cross-sectional
area of a bed in an annular basket, h—height of the bed), porosity 50% (3 mm extrudates)
Appl. Sci. 2023, 13, x FOR PEER REVIEW 7 of 28
and 60% (8 mm tablets). Operating parameters of the catalytic reactor: p = 450 kPa abs.,
T = 673 K.

Figure1.1.The
Figure Thedependence
dependenceofofthe
thetail-gas
tail-gaspressure
pressure drop
drop across
across thethe deNO
deNO x catalyst beds in the form
x catalyst beds in the form of
of extrudates (ϕ = 3 mm) and tablets (ϕ = 8 mm) on the linear gas flow velocity
extrudates (φ = 3 mm) and tablets (φ = 8 mm) on the linear gas flow velocity (own (own research).
research).

The influence of the catalyst shaped body dimensions, bed porosity, shape factor and
linear gas flow velocity on the pressure drop value can be determined based on the Ergun
Equation (10):
∆ ( ) ( )
=A +B (15)

H—height of the catalyst bed, m

ΔP—pressure drop of a gas flow through the catalyst bed, Pa
Appl. Sci. 2023, 13, 7492 7 of 27

The influence of the catalyst shaped body dimensions, bed porosity, shape factor and
linear gas flow velocity on the pressure drop value can be determined based on the Ergun
Equation (10):
−∆P µV(1 − ε)2 ρf V2 (1 − ε)
=A + B (15)
H x 2 ε3 xε3
H—height of the catalyst bed, m
∆P—pressure drop of a gas flow through the catalyst bed, Pa
V—linear gas flow velocity, m/s
x—hydraulic diameter of the shaped catalyst body, m
ε—bed porosity,
ρf —density of the gas flowing through the catalyst bed, kg/m3 ,
µ—gas viscosity, Pa·s.
For the shaped catalyst bodies, slightly differing from the shape of a sphere, the
Blake–Kozeny–Carman and Plummers coefficients are equal to A = 150 and B = 1.75. The
hydraulic diameter can be determined from Equation (16):

6Vi
x= (16)
Si

Vi —volume of the shaped catalyst body, m3

Si —surface of the shaped catalyst body, m2 .
The average catalyst bed porosity can be determined based on the volume of the
catalyst bed, mass and density of the shaped catalyst body, according to Equation (17):
mw
Vtot − ρw
ε= (17)
Vtot

The higher gas flow resistances promote better gas distribution over the catalyst bed.
On the other hand, it is associated with less energy recovery in the expansion turbine, which
translates into higher operating costs. The linear gas flow velocity affects the rate of catalytic
reaction that runs in the diffusion regime, i.e., in the presence of the shaped catalyst. By
lowering it, the efficiency of the deNOx and deN2 O processes can be increased [26,61–65].
When developing the technology for the tail gases purifying from nitrogen oxides, the
following aspects should be taken into account: the minimum N2 O and NOx conversion
expected by the industrial customer, or required to meet the applicable emission standards,
the allowable pressure drop across the catalyst bed, and in case of using reducers, their
permissible concentration in the purified gas stream (e. g. ammonia slip). On this basis,
it is possible to select the appropriate type and/or shape of catalysts for N2 O decomposi-
tion/reduction and NOx reduction, and determine the catalytic reactor design. The design
of the reactor interior determines the value of the gas pressure drop across the catalyst
bed and the linear gas flow velocity through the bed, which influences the efficiency of
the catalyst operation. The assumed permissible pressure drop values across the catalyst
bed are: ≤0.005 bars for low-pressure nitric acid plants (0–2 bars), ≤0.015 bar for the
medium-pressure (3–6 bars), and ≤0.1 bar for the high-pressure ones (7–12 bars) [66].

3. Various Aspects of Designing Reactors for Purifying the Tail Gases from N2 O
and NOx
Several aspects should be considered when designing a reactor for the nitrogen oxides
removal from the tail gases emitted from nitric acid plants:
• The required reactor size (dependent on a gas flow rate and catalyst activity);
• The gas temperature at the reactor inlet, required for the effective catalyst operation
(eventually, selection of a heat exchanger for the tail gases preheating before they enter
the catalytic reactor);
• The allowable gas flow resistances across the catalyst bed;
Appl. Sci. 2023, 13, 7492 8 of 27

• Permissible content of nitrogen oxides downstream of the deNOx /deN2 O reactor;

• Method of the tail gases purifying from the nitrogen oxides (selective or non-selective
catalytic reduction of N2 O, direct catalytic N2 O decomposition);
• The method of mixing the tail gases with a reducing agent (selection of the static mixer)
and distributing of this mixture inside the reactor [67,68];
• The arrangement (sequence) of the catalyst beds in reactors for simultaneous purifying
of the tail gases from N2 O and NOx and a method of reducing agent introduction
upstream of the second catalyst bed;
• The available free space in the technological line of HNO3 plant, in which the reactor
could be installed (downstream of the absorption column).
The process of reactors designing is often supported by numerical calculations (CFD—
Computational Fluid Dynamics). They allow for optimising the proposed solution or
determining the distribution of gas velocity, pressure and temperature or the degree of
reactants conversion within the reactor volume for different reactor design solutions. The
CFD method enables to simulate the influence of key process parameters on the efficiency
of the NOx reduction process, such as temperature, NH3 /NOx molar ratio and GHSV.
Ansys Fluent, OpenFOAM, or Comsol Multiphysics software can be used to simulate the
gas flow throughout the reactor. When building a reactor model that would best reflect
the actual process conditions, the following factors should be taken into account: reactor
design, the process of ammonia with the tail gases mixing, mass and heat transfer processes
in a multi-component system, as well as the main chemical reactions. Due to the slight
temperature difference between the outlet and inlet of the reactor, the modelled system
can be treated as an adiabatic. The computational domain, reflecting the interior of the
modelled reactor, is built based on the spatial dimensions of the existing or designed reactor
(2D axisymmetric modelling or 3D modelling in the COMSOL program). It is divided
into many subdomains, within which the CFD equations are discretized (e.g., by GAMBIT
software) and calculated. It is crucial to select the correct geometry of the mesh elements
(e.g., cuboid, tetrahedron, prism, pyramid), the number of subdomains and their sizes,
which affect the accuracy of the calculations. The computational mesh is densified in
the area of higher turbulence. Then, boundary, initial and operating conditions (based
on industrial practice) are determined. The model parameters can be determined from
the experimental results, using an optimization procedure based on a Taguchi method
(used to design the experiment), a real-coded genetic algorithm (to search for optimal
solutions) and a shape-tunable neural network (to bind the operational data together). The
gas flow through the catalyst bed can be modeled as a compressible and viscous fluid flow
through a porous medium. A k-ε turbulent flow model, e.g., of the RANS type (Reynolds-
Averaged Navier–Stokes), as well as the equations of continuity and conservation of mass,
momentum and energy can be used. The fixed bed reactors are modelled as a plug flow or
axially dispersed plug flow. The gas density, dynamic viscosity, temperature, pressure and
composition are determined based on the characteristics of the real gas. For most catalyst
beds, the gas flow is considered as turbulent, except for the flow inside the monolith chanels,
where it is treated as laminar. The main chemical reactions rates, involving NO and NH3
reactants, can be determined using the Chae kinetic model. To consider the reactor porosity,
i.e., to obtain information on the permeability and pressure drop across the catalyst bed,
the Ergun, Darcy–Forchheimer or Brinkman equations are also applied. The pressure
equation can be obtained by combining continuity and momentum conservation equations.
To solve the equations mentioned above, the appropriate solvers are used, depending
on the nature of the fluid flow (laminar or turbulent, compressible or incompressible),
the type and quantity of flowing media or the degree of gases mixing. A possible heat
exchange should also be taken into account. The examples of solvers, that can be used, are:
linear and non-linear solvers (pressure-based or density-based), fully coupled stationary
solver with Direct module—UMFPACK, PCG—preconditioned (bi)-conjugate gradient
solver for symmetric matrices, PbiCG—preconditioned stabilized (bi)-conjugate gradient
solver for arbitrary matrices, smooth Solver—function smoothing, GAMG solver—using a
 Appl. Sci. 2023, 13, 7492 9 of 27

generalized multi-mesh geometric-algebraic method, diagonal—for explicit methods, DIC

with buffering—accelerated incomplete Choleski factorization, etc. [58,63,65,69–71].
The deNOx /deN2 O reactor is a vertical apparatus installed on a steel supporting
structure, inside which the catalyst bed is installed. Depending on the route of the tail gases
pipeline and the available space in the technological line of nitric acid manufacturing, the
arrangement of the reactor can be downflow or upflow. The gas inlet and outlet can be
located in the upper and lower part of the reactor or on its side wall. Inside the reactor, the
following zones can be distinguished:
- Reducing agent injection (this zone can be located upstream of the reactor or inside it);
- Reactor inlet with possible internal elements improving gas flow distribution over the
catalyst bed or tail gases mixing with reducing agent;
- Reaction zone with the catalyst bed;
- Reactor outlet.
The efficiency of the SCR process is more remarkable the more homogeneous the gas
flow field inside the reactor, and the more even the ammonia concentration distribution in
the tail-gas stream. NH3 concentration profile in the tail-gas stream should be similar to
the NOx concentration profile. To ensure a homogeneous gas flow field (conditioning of
the gas flow) upstream of the catalyst bed, perforated plates, baffle plates, rectifying grids,
guide vanes/plates or flow rectifiers are often installed inside the reactor. In the ammonia
injection zone, static mixers can be installed. Flow rectifiers are used to ensure such a
ratio value of the channel opening hydraulic diameter to the length of the gas flow path to
create vertical flow lines upstream of the catalyst bed. Static mixers affect the flow structure
by generating secondary cross-flow vortices and turbulent flow, increasing the mass and
heat transfer in the cross-section of the pipeline/reactor while maintaining low-pressure
drops. It can be a hollow pipe with openings or a channel with baffles mounted inside:
straight, angled, corrugated or helical (Komax Custody Transfer, Kenics, Ross Engineering,
Chemineer, Sulzer, JLS International). Static mixers can be of various types, e.g., made of
metallic foam or suitably shaped sheets installed in the inlet section of the reactor (Iso Swirl,
OR PEER REVIEW Shear, Swirl-Shear and Vortex mixers) [72–76]. 10 of 28
Figure 2a,b show two simple static mixers: a pipe with holes and a helix-shaped sheet
mounted inside the pipe. The red arrow marks the inlet of the reducing agent.

(a) (b)
Figure 2. Two types Figure
of static mixers:
2. Two types(a) a pipe
of static with(a)
mixers: holes;
a pipe(b)
witha holes;
helix-shaped sheet. The
(b) a helix-shaped inlet
sheet. Theof
inlet of
ammonia is marked with a redis arrow.
ammonia The atail
marked with redgases
arrow.flow through
The tail thethrough
gases flow main pipe.
the main pipe.

The catalyst bed is mounted on a supporting steel structure in the reaction zone. It
consists of load-bearing elements, permanently fixed to the reactor wall, and a basket
resting on them. The shape of the catalytic basket is usually cylindrical, annular or a
rectangular cassette. In the case of the axial tail-gas flow, it can also be a perforated plate
placed at the bottom of the reactor. The design of the catalytic basket should ensure even
Appl. Sci. 2023, 13, 7492 10 of 27

The catalyst bed is mounted on a supporting steel structure in the reaction zone. It
consists of load-bearing elements, permanently fixed to the reactor wall, and a basket
resting on them. The shape of the catalytic basket is usually cylindrical, annular or a
rectangular cassette. In the case of the axial tail-gas flow, it can also be a perforated plate
placed at the bottom of the reactor. The design of the catalytic basket should ensure even
gas distribution over the catalyst bed and mechanical integrity of the supporting structure.
It should also enable the catalyst bed to be maintained stable throughout the entire period
of operation and be resistant to rapid temperature changes or thermal shock (especially
during emergency shutdowns of the plant). The catalytic basket may also contain vertical
or diagonal plates, forcing a change in the flow direction of the gas stream.
When designing the reactors, the stresses of the reactor’s elements, natural frequency,
local and general buckling modes induced by uniform compressive, bending and shear
forces should be considered. deNOx and deN2 O reactors are subject to thermal expansion,
contraction and vibrations caused by the gas flow or operation of various devices in their
immediate vicinity. The choice of reactor construction materials depends on the required
material strength, corrosion resistance and process economy. The key parameters of the
steel are a creep and fatigue strength and yield strength under process conditions, which are
mainly temperature dependent. If the steel temperature does not exceed 454 ◦ C, ordinary
carbon steel can be chosen as the reactor construction material (above this temperature,
steel graphitization occurs and the creep strength decreases). If it is higher, low-alloy steels
with the addition of chromium and molybdenum should be considered. AISI-304L steel is
often selected as the construction material for deNOx /deN2 O reactors. A-387 alloy steel can
also be used due to its resistance to creep, graphitization and oxidation. The reactor should
be insulated from the environment to maintain the temperature of its walls above the dew
point temperature of HNO3 (protection against corrosion when the nitric acid plant is shut
down). The insulation also protects the hot reactor surface against contact with cold water
from the rain (the material is then susceptible to bending and cracking) [72,74,75,77–80].
The choice of the reactor type depends on several factors: the rate of a chemical
reaction under given process conditions, heat transfer, the influence of external diffusion
resistance on the catalyst selectivity and the degree of reactants conversion. The main types
of fixed bed deNOx /deN2 O reactors used in nitric acid plants are axial, radial and lateral.

3.1. Axial Flow Reactor

The gas stream flows through the catalyst bed parallel to the reactor axis in axial flow
reactors. The catalyst bed is installed in a cylindrical basket or on a perforated plate placed
at the bottom part of the reactor. This design allows more space inside the reactor for the
catalyst bed installation. If a cylindrical basket is used, it is necessary to seal it around the
reactor perimeter to avoid gas by-passing.
The use of a seal is not required when the catalyst bed rests on a perforated plate and
is in contact with the side walls of the reactor. Figure 3a,b show an exemplary interiors of
the deNOx /deN2 O reactor, with the construction that forces the axial flow of the tail-gas
stream through the catalyst bed. The black arrow shows the direction of the purified gas
flow schematically. A perforated plate, installed upstream of the catalyst bed (1), is used to
improve gas distribution over the catalyst bed.
To increase the gas purification efficiency in an axial flow reactor, without increasing
the gas flow resistances, the diameter of the reactor should be increased. However, this
requires using a thicker, heavier and more expensive reactor shell, which will be subject to
faster exploitation. When designing a reactor with a larger diameter, the plant’s production
capacity and the efficiency of the media transport equipment should be considered.
The advantages of the axial flow reactor are the easy loading and unloading of the
catalyst and the simple design of the catalytic basket. With the same space inside the
reactor, a larger catalyst bed volume can be installed in the cylindrical basket compared
to the other solutions (described below). It is due to the absence of additional baffles and
empty spaces, constituting the zone of the gas inflow onto the catalyst bed. Reactors with
 3.1. Axial Flow Reactor
The gas stream flows through the catalyst bed parallel to the reactor axis in axial flow
reactors. The catalyst bed is installed in a cylindrical basket or on a perforated plate placed
at the bottom part of the reactor. This design allows more space inside the reactor for th
Appl. Sci. 2023, 13, 7492 catalyst bed installation. If a cylindrical basket is used, it is necessary to seal11itofaround
27 th
reactor perimeter to avoid gas by-passing.
The use of a seal is not required when the catalyst bed rests on a perforated plate and
aisdesign that forces
in contact the axial
with the gas flow
side walls through
of the the catalyst
reactor. bed generate
Figure 3a,b show angreater pressure
exemplary interiors o
drops compared with reactors in which the gas flows through the bed perpendicular to the
the deNOx/deN2O reactor, with the construction that forces the axial flow of the tail-ga
reactor axis (radial or lateral flow). In addition, they are characterized by a higher linear
stream through the catalyst bed. The black arrow shows the direction of the purified ga
gas flow velocity, which translates into a lower conversion of nitrogen oxides in relation to
flow
the schematically.
radial A perforated
or lateral flow plate,
reactor. In the axialinstalled upstream
flow reactor, of thedrop
the pressure catalyst bed (1), is used
and catalyst
to improve
efficiency cangas distribution
be influenced over the catalyst
by changing the form bed.
and size of the shaped catalyst body.

(a) (b)
Figure3.3.Reactor
Figure Reactor forfor heterogeneous
heterogeneous catalytic
catalytic processes
processes with awith a structure,
structure, thatthe
that forces forces
axial the
gas axial ga
flowthrough
flow throughthethe catalyst
catalyst bed.bed. (a) Reactor
(a) Reactor interior
interior with anwith an empty
empty catalyticcatalytic basket: 1—perforated
basket: 1—perforated
plateimproving
plate improving mixing
mixing of ammonia
of ammonia withwith thegases,
the tail tail gases, 2—bottom
2—bottom perforated
perforated basket
basket wall, wall, 3—solid
3—solid
sidewall
side wallofof
thethe basket.
basket. (b) (b) Catalytic
Catalytic basket
basket with awith
doublea double catalyst/s
catalyst/s bed: A—deNO
bed: A—deNO x catalyst
x catalyst bed
bed,
B—deN O catalyst
B—deN2 O catalyst bed.
2 bed.

InToaxial flow reactors,

increase the gasmonolithic catalysts
purification can beininstalled
efficiency an axial(e.g.,
flow CuO-NiO
reactor,on a ceramic
without increasing
monolith based on alumina-silicates, BASF O4-85 catalyst based on vanadium oxide) with-
the gas flow resistances, the diameter of the reactor should be increased. However, thi
out fear of too-high pressure drops. Their specific “architecture” enables high efficiencies
requires using a thicker, heavier and more expensive reactor shell, which will be subjec
of the tail gases purifying from nitrogen oxides at the low pressure drops [61,65,81–85].
to faster exploitation.
When using a dual-bed When designing
catalytic a reactor
system, e.g., deNOx /deN with O, a the
larger diameter,
catalyst beds canthe
be plant’
2
production capacity and the efficiency of the media transport equipment
installed inside one catalytic basket and separated from each other by a perforated plate or should b
considered.
gauze (mesh size should be smaller than the size of the shaped catalyst body). The deNOx
The
catalyst bedadvantages of theinaxial
should be placed flow part
the upper reactor are
of the the easy
catalytic loading
basket, whileand unloading of th
the ammonia
is mixed with the tail gases before entering the reactor. If the arrangement
catalyst and the simple design of the catalytic basket. With the same space of the catalyst
inside th
beds is changed, they should be separated from each other by a space, into which
reactor, a larger catalyst bed volume can be installed in the cylindrical basket compared gaseous
ammonia is introduced and mixed with the tail-gas stream. The gaseous ammonia pipeline
to the other solutions (described below). It is due to the absence of additional baffles and
would then be installed on the side wall of the reactor. Ammonia could be introduced into
empty spaces, constituting the zone of the gas inflow onto the catalyst bed. Reactors with
the gas stream using an ammonia injection grid.
a design that forces the
The construction axial
of the gas flow
catalytic through
reactor, the catalyst
operating bed flow
in the axial generate
mode, greater
can bepressur
drops compared with reactors in which the gas flows through the
easily converted into the axial–radial or radial flow mode, without significantly modify- bed perpendicular to
thethe
ing reactor
reactoraxis (radial
interior. or modification,
Such lateral flow).however,
In addition,
reduces theytheare characterized
space available for by
thea highe
linear gas
catalyst bed.flow velocity, which translates into a lower conversion of nitrogen oxides in
relation to the radial or lateral flow reactor. In the axial flow reactor, the pressure drop
3.2. Radial Flow Reactor
The radial gas flow reactor has a more complex design than the axial flow one and the
catalytic basket has an annular shape. The side walls of the basket are perforated, while
 Appl. Sci. 2023, 13, 7492 12 of 27

its lower part is gas-impermeable. After loading the catalyst into the basket, a solid top
cover plate is installed, the side walls of which are usually several centimetres high. They
protect the basket against gas bypassing in the event of catalyst bed settling (e.g., due to
catalyst sintering or settling the bed under its weight). The gas stream entering the reactor
first flows in the axial direction, and it hits the top cover plate of the catalytic basket. Then,
it enters the annular space between the reactor wall and the side wall of the basket. It flows
radially through the catalyst bed into the central tube, through which it exits the reactor.
The gas flow through the catalyst bed should be mainly radial, preferably with no axial
velocity component. The share of axial velocity components may cause an effect similar
to “back-mixing”, reducing the gas purification efficiency (mixing of gas streams with
different degrees of reactants conversion). In radial flow reactors, two gas flow directions
are possible: from the central part of the reactor towards its side walls or from the annular
space between the basket and the reactor side wall to the central part of the reactor, through
which the gas leaves it.
Figure 4a,b show the interior of a radial reactor with a single empty annular catalytic
basket and two annular catalytic baskets with NOx and N2 O catalyst beds. The black
arrows show one of the possible directions of the gas flow through the catalyst basket. The
tail gases mixed with the reducing agent are fed to the reactor through the inlet. A large
part of the gas stream hits the top cover plate of the catalytic basket and changes direction.
Then, it enters the space between the reactor and basket side walls. The gas stream flows
radially through the annular-shaped catalyst beds to the central pipe and exits the reactor
at the outlet. The inner side wall of the outer annular basket is simultaneously the outer
Appl. Sci. 2023, 13, x FOR PEER REVIEW
side wall of the inner annular basket. To ensure radial flow, the bottom part of the catalytic
basket is gas-impermeable, and the upper part is closed by the top cover plate, while the
side walls are perforated.

(a) (b)
Figure
Figure 4.4.Reactor
Reactorforfor heterogeneous
heterogeneous catalytic
catalytic processesprocesses with athat
with a structure structure thatgas
forces radial forces
flow radial g
through
through thethecatalyst
catalystbed.bed. (a)—basket
(a)—basket with onewith one space,
annular annular space,one
in which incatalyst
whichbed onecancatalyst
be bed
installed: 1—perforated
installed: 1—perforated plateplate
improving gas flowgas
improving distribution and mixing,and
flow distribution 2—solid top cover
mixing, plate, top cov
2—solid
3—outer perforated
3—outer perforated sideside
wallwall
of theof
basket, 3a—perforated
the basket, inner side wall
3a—perforated of the
inner sidebasket,
wall 4—solid
of the basket,
bottom plate of the basket. (b)—dual-bed catalytic system: A—deNOx catalyst bed, B—deN2 O
bottom plate of the basket. (b)—dual-bed catalytic system: A—deNOx catalyst bed, B—
catalyst bed.
catalyst bed.

When designing radial flow reactors, certain conditions should be taken into a
• It is necessary to ensure uniform gas distribution over the catalyst bed, alo
entire length of the catalytic basket to achieve higher nitrogen oxide con
Appl. Sci. 2023, 13, 7492 13 of 27

When designing radial flow reactors, certain conditions should be taken into account:
• It is necessary to ensure uniform gas distribution over the catalyst bed, along the entire
length of the catalytic basket to achieve higher nitrogen oxide conversion (uneven gas
distribution results in uneven exploitation of the catalyst bed and basket, which may
lead to corrosion);
• Settling of the catalyst bed during operation may result in an empty space formation in
the upper part of the bed and gas bypassing. In total, 5–20% excess of the catalyst bed
should be used in relation to the amount required to achieve the assumed nitrogen
oxides conversion, compensating for bed settlement. This amount depends on
the mechanical properties of the catalyst and the number of plant shutdowns and
start-ups;
• In a radial reactor, a sufficient space between the reactor and the basket side wall
should be ensured to distribute the gas stream over the catalyst bed evenly;
• When two or more catalyst beds are used, the deNOx catalyst bed should be placed in
the outer annular basket (inward flow of the gas stream). In a radial flow reactor with
a co-axial arrangement of the annular catalytic baskets along the reactor diameter, it is
not possible to introduce a reducing agent upstream of the second catalyst bed.
Radial flow reactors can be used for high gas flow rates through the catalyst bed, where
it is required to purify large amounts of gas per unit time while ensuring low pressure drops.
This reactor provides lower gas flow resistances across the catalyst bed, compared with the
axial ones, for the same volumetric gas flow rate. The efficiency of tail-gas purification from
the nitrogen oxides in the radial reactor can be increased by increasing the reactor length.
Despite the greater height of the bed, its lower thickness ensures a lower gas pressure drop.
Such a reactor design enables the use of smaller sizes of the shaped catalyst bodies, which
allow increasing the efficiency of the deNOx /deN2 O technology without fear of excessive
pressure drop.
In a radial reactor, the catalyst bed settles during operation, and an empty space may
form in the upper part of the bed, constituting a path of gas bypassing. It is, therefore,
important to seal the catalyst bed in this area so that the gas does not reach the upper edge
of the catalyst bed in the catalytic basket. The upper part of the catalyst bed is usually
shielded by a gas-impermeable top cover plate. This part of the bed serves as a seal and is
not used in gas purification. Using an excess catalyst as a sealing layer increases the cost
of the apparatus and the deNOx /deN2 O technology. Using a top cover plate of suitable
weight and design also generates additional costs compared with the axial reactor.
The radial reactor provides more efficient use of the available reaction zone than the
axial one, while lower pressure drops translate into higher energy recovery in the expansion
turbine. This design also has disadvantages. Catalyst loading and unloading in the radial
reactor is more complicated and time-consuming. In addition, there is a need to install or
remove the basket’s top cover plate. Due to the low gas flow resistances, there can also
be a problem with the uniform gas distribution over the catalyst bed, along the length of
the reactor. Thus, the longer the reactor is, the poorer the gas distribution along the height
of the basket. A way to slightly increase the flow resistance is to use a suitable design of
basket walls in the upper and lower part of the catalyst bed. They should ensure a higher
gas flow resistance in the upper part of the catalyst bed (near the top cover plate) and lower
gas flow resistance in the lower part of the catalyst bed. This reduces gas recirculation in
the annular space between the reactor and perforated side walls of the basket, as well as in
the central part of reactor. The gas flow resistance through the perforated basket walls can
be varied by, e.g., the use of different hole sizes and varying their location (the basket walls
can be made of Vee Wire or Johnson screens).
Radial reactors are often offered to nitric acid producers by BASF as part of the SCR-
deNOx technology. Most often, catalysts based on vanadium oxide on TiO2 support or
iron-modified zeolites in the form of extrudates are installed in them [35,61,65,80,84,86–89].
 Radial reactors are often offered to nitric acid producers by BASF as part of
deNOx technology. Most often, catalysts based on vanadium oxide on TiO2 su
iron-modified zeolites in the form of extrudates are installed in them [35,61,65,80,8
Appl. Sci. 2023, 13, 7492 14 of 27
Radial Flow Reactor with Triple-Bed Catalytic System
The catalyst beds in the radial flow reactor can be installed in the three
Radial Flow Reactor with Triple-Bed Catalytic System
baskets, arranged coaxially along the reactor’s diameter and/or axis. Casale propo
The catalyst beds in the radial flow reactor can be installed in the three annular
a solution. It consists of a three-stage tail-gas purification from the nitrogen oxid
baskets, arranged coaxially along the reactor’s diameter and/or axis. Casale proposed such
a reactor, including
solution. It consists ofNO x reduction with ammonia on the first and third catalytic
a three-stage tail-gas purification from the nitrogen oxides in one
N2O decomposition
reactor, on thewith
including NOx reduction second
ammoniacatalytic
on thebed. This
first and solution
third catalyticmay
beds be
andadvanta
Niron-modified
2 O decomposition zeolite
on the catalysts
second are used
catalytic bed.in deN
This O process,
solution
2 may for
be which the
advantageous co-cataly
if
iron-modified zeolite catalysts are used
of the NOx presence on N2O decomposition in deN 2 O process, for which
has been found.the co-catalytic effect
of the NOx presence on N2 O decomposition has been found.
Figure 5 shows an exemplary arrangement of deNOx and deN2O catalyst b
Figure 5 shows an exemplary arrangement of deNOx and deN2 O catalyst beds in a
radial
radial reactor,
reactor, according
according to thesolution.
to the Casale Casale solution.

Figure 5. Radial reactor with triple-bed catalytic system, with catalytic beds arranged co-axially
along the reactor’s diameter and axis: A—deNOx catalyst bed, B—deN2 O catalyst bed (based on
patent [56]).

The direction of the tail-gas flow across the reactor is shown by black arrows. The
reducing agent is introduced into the tail-gas stream upstream of the first and third catalyst
beds. On the first deNOx catalyst bed, the NOx content in the gas stream is reduced to
50–200 ppm. The presence of these oxides upstream of the second catalyst bed increases
the efficiency of N2 O decomposition (the following reaction occurs: NO + N2 O → NO2 +
N2 ). The tail-gas stream leaving the deN2 O catalyst bed is collected in a central collector,
to which another portion of the reducing agent, necessary to reduce NOx concentration to
25 ppm, is introduced.
The use of the Casale solution allows for reducing NOx (vanadia-titania or Fe-zeolite
catalyst) and N2 O (Fe-zeolite catalyst) emissions to the levels of <25 ppm and <30 ppm
(efficiency >95%), respectively, with ammonia slip no greater than 2 ppm. Its advantage is
the more efficient use of the reducing agent (ammonia) and the possibility of using part
of the NOx amount in the N2 O decomposition process. The disadvantage is the complex
design of the reactor, which hinders the operation of loading and unloading catalysts to the
baskets. Additionally, the ammonia injection/dosing, and the control and measurement
system are more complex. It is necessary to install two separate ammonia injection zones,
use an additional measurement point of NH3 and NOx concentration in the tail-gas stream
 the baskets. Additionally, the ammonia injection/dosing, and the contr
measurement system are more complex. It is necessary to install two separate am
injection zones, use an additional measurement point of NH3 and NOx concentr
the tail-gas stream (between the second and third catalyst beds), as well as anoth
Appl. Sci. 2023, 13, 7492 15 of 27
device to control the amount of ammonia introduced upstream of the third catal
[56,90].
Thethe
(between radial
second reactor, with
and third a construction
catalyst beds), as wellsimilar to other
as another the Casale solution,
device to control the can also
in the EnviNO
amount of ammonia x technology. Figure of
introduced upstream 6a,b
the show an exemplary
third catalyst bed [56,90].arrangement of deN
The radial reactor, with a construction similar
deN2O catalyst beds for the first and second variants of the to the Casale solution,
EnviNO canx processes.
also be In
used in the EnviNOx technology. Figure 6a,b show an exemplary arrangement of deNOx
case, a mixture of ammonia and tail gases are introduced into a catalytic reac
and deN2 O catalyst beds for the first and second variants of the EnviNOx processes. In
directed to athe
the first case, deNO
mixture catalystand
ofxammonia bed.tailAfter reducing
gases are theinto
introduced NOaxcatalytic
, the gas flows throu
reactor
deN 2O catalyst
and directed to the bed,
deNOwhere
x catalystdirect catalytic
bed. After N2O
reducing thedecomposition
NOx , the gas flowsoccurs.
throughThe use
deNO
the deN x 2process
O catalyst inbed,
the where
first stage
directofcatalytic
tail-gasN2purification
O decompositionis advantageous.
occurs. The useAs of a resul
the deNO process in the first stage of tail-gas purification is advantageous.
process, the temperature of the purified gas increases before it enters the deN2O
x As a result
of this process, the temperature of the purified gas increases before it enters the deN2 O
bed.
catalyst bed.

(a) (b)
Figure 6. Radial flow reactors with a dual-bed catalytic system, where catalyst beds are arranged
coaxially along the reactor axis. It can be used in the first variant (a) or the second variant (b) of
EnviNOx processes. A—deNOx catalyst bed, B—deN2 O catalyst bed.

For the second variant of the EnviNOx process, the deN2 O catalyst bed is installed in
the upper annular catalytic basket, while the deNOx catalyst is installed downstream of the
deN2 O catalyst bed. In this case, it is necessary to use two types of reducing agents, so there
are two possibilities. Hydrocarbon and tail-gas mixtures are introduced into the reactor to
reduce N2 O on the first catalyst bed, while ammonia (for NOx reduction) is introduced into
the space between the deN2 O and deNOx catalyst beds (Figure 6b). Another possibility is
to introduce a mixture of tail gases with both reducing agents. Figure 6 shows one possible
way of injecting ammonia into the gas stream. It is also possible to install an ammonia
injection grid inside the reactor, upstream of the deNOx catalyst bed. NH3 could then be
supplied through a pipeline installed on a side wall of the reactor.

3.3. Radial Flow Reactor with Deflectors

The flow direction in a radial flow reactor can be modified by introducing a deflector
in the central part of the reactor and in the spaces between the catalyst beds (in case of
using more than one concentric annular basket inside the reactor). Figure 7a,b show a radial
flow reactor with several annular deNOx and deN2 O catalyst beds and deflectors arranged
 The flow direction in a radial flow reactor can be modified by introducing a d
in the central part of the reactor and in the spaces between the catalyst beds (in
using more than one concentric annular basket inside the reactor). Figure 7a,b
Appl. Sci. 2023, 13, 7492 radial flow reactor with several annular deNOx and deN2O catalyst beds 16 of 27 and de

arranged between them. The deflectors direct the gas stream radially through the
beds without generating significant gas flow turbulence and ensure unifo
between them. The deflectors direct the gas stream radially through the catalyst beds
distribution over the catalyst bed. The central deflector has the shape of an inverte
without generating significant gas flow turbulence and ensure uniform gas distribution
while
over the the otherbed.
catalyst deflectors have
The central a form
deflector ofthe
has a truncated
shape of ancone with
inverted a parabolic
cone, while the outer
The
other lower edge
deflectors haveofa form
theseofdeflectors is connected
a truncated cone to the
with a parabolic lower
outer edge
surface. Theoflower
the inner
edge of these deflectors is connected to the lower edge of the inner
basket with the catalyst bed. The upper edge of the deflectors is connected annular basket with the to th
catalyst bed. The upper edge of the deflectors is connected to the upper
edge of the outer annular basket. The deflector extends from the upper edge of theedge of the outer
annular basket. The deflector extends from the upper edge of the catalyst bed to the lower
bed
edge to theadjacent
of the lower edge
catalystofbed.
the adjacent catalyst bed.

(a) (b)
Radial flow
Figure 7.7. Radial
Figure flowreactor
reactorwith
withdeflectors for heterogenous
deflectors catalytic
for heterogenous processes
catalytic (based on(based o
processes
patent1—solid
[91]): [91]): 1—solid
plateplate constitutingthe
constituting thebottom
bottom part
partofofthe
thebasket, 2—deflectors,
basket, 3—perforated
2—deflectors, 3—perforated s
side wall of the basket, 4—gas-impermeable upper wall of the basket,
of the basket, 4—gas-impermeable upper wall of the basket, A and B—deNO A and B—deNO x (a) xand
(a) and de
deN2 O (b) catalyst beds.
catalyst beds.
The purified gas stream, fed to the reactor’s lower stub pipe, flows into the space
between the catalyst beds, where it is deflected by the deflector walls and directed radially
through the catalyst bed. Then, the gas stream is deflected on the outer wall of the next
deflector and flows to the reactor outlet.
Compared with a classic radial flow reactor, the deflectors make it possible to extend
the flow path of the gas before it enters the catalyst bed. This improves gas distribution over
the catalyst beds, along the reactor axis, and ensures a gentle inflow of the gas stream onto
the bed. The pressure drops across the catalyst bed in a radial-flow reactor with deflectors
are about ten times lower than in the axial one, using the same total volume as the catalyst
bed. However, additional elements in the form of deflectors are also an expensive option.
So far, this type of reactor has been used for purifying the tail gases generated in the
fuel combustion processes [91].

3.4. Radial–Axial Flow Reactors

Many methods of deNOx and deN2 O catalyst beds arrangement in the reactor for
purifying the tail gases from nitrogen oxides are described in the patent literature. These
are mainly ThyssenKrupp Uhde and Casale solutions. Some of them concern the use of
 Appl. Sci. 2023, 13, 7492 17 of 27

two different catalyst bed configurations, forcing the gas stream to flow in both radial and
axial directions.
Figure 8a,b show two variants of the catalytic reactor in a longitudinal section with
two catalyst beds. The black arrows indicate the direction of the gas flow. In the first case,
the tail gases mixed with ammonia are introduced onto the deNOx catalyst bed, which
forces it to flow in the axial direction (the upper and lower part of the catalytic basket is
perforated, while the side walls are gas-impermeable). The tail-gas stream, purified at the
first stage from NOx , flows to a space surrounded by the deN2 O catalyst bed installed in
the annular basket. The side walls of the basket are perforated, while the top and bottom
parts are gas-impermeable. The gas stream flows radially through the deN2 O catalyst bed
from the central part of the reactor towards its side walls and is directed to the outlet. This
type of reactor could be used for conducting the EnviNOx process according to variant
Appl. Sci. 2023, 13, x FOR PEER REVIEW
II. In this case, tail gases mixed with ammonia would be fed to the reactor (the first gas
purification stage—deNOx process). A hydrocarbon would be introduced into the tail gases
upstream of the second bed—deN2 O catalyst.

(a) (b)
Figure8. 8.
Figure Reactors
Reactors for conducting
for conducting heterogeneous
heterogeneous catalytic
catalytic reaction with the reaction with the
dual-bed catalytic dual-bed
system
(A—deNO x catalyst bed,
system (A—deNO B—deN2 O
x catalyst catalyst
bed, B—deNbed), 2forcing the gasbed),
O catalyst to flow both in the
forcing the axial
gas and radialboth in
to flow
direction:
and radial (a)—axial–radial flow, (b)—radial–axial
direction: (a)—axial–radial flow, flow (based on patent [35,92]).
(b)—radial–axial flow (based on patent [35,92]
The second variant of the catalytic reactor (Figure 8b) could be used in the I variant of
The flow
the EnviNO of the tail gases in the axial–radial direction can also be realized by in
x process. The tail gases initially flow along the reactor axis, hit the top cover
the annular
plate and enter baskets
the annularcoaxially alongthe
space between the reactor
reactor diameter side
and perforated (Figure
walls 9). Contrary
of the
catalytic basket. The tail gases flow radially through the deN O catalyst
solutions presented in Figure 8a,b, both catalyst beds (deNOx and deN2O) are inst
2 bed, on which
direct catalytic N2 O decomposition occurs. In the central collector, they are mixed with
the annular catalytic baskets. The side walls of the catalytic baskets and the top p
ammonia and directed axially to the deNOx catalyst bed, placed in a cylindrical basket.
perforated,
In while
Figure 8b, one the
of the bottom
methods of walls are gas-impermeable.
introducing ammonia to the spaceThe first the
between catalyst
two bed i
outer basket
catalyst beds is and
shown the upper
(pipe withpart ofItthe
holes). caninner
also beannular basket.
an ammonia injection grid.
The flow of the tail gases in the axial–radial direction can also be realized by installing
the annular baskets coaxially along the reactor diameter (Figure 9). Contrary to the solutions
 Figure 8. Reactors for conducting heterogeneous catalytic reaction with the dual-bed
system (A—deNOx catalyst bed, B—deN2O catalyst bed), forcing the gas to flow both in
and radial direction: (a)—axial–radial flow, (b)—radial–axial flow (based on patent [35,92

Appl. Sci. 2023, 13, 7492 The flow of the tail gases in the axial–radial direction can also be 18 realized
of 27 by i
the annular baskets coaxially along the reactor diameter (Figure 9). Contrar
solutions presented in Figure 8a,b, both catalyst beds (deNOx and deN2O) are ins
presented in Figure
the annular 8a,b, both
catalytic catalyst The
baskets. beds side
(deNO x and deN
walls 2 O) catalytic
of the are installed in the annular
baskets and the top
catalytic baskets. The side walls of the catalytic baskets and the top plate are perforated,
perforated, while the bottom walls are gas-impermeable. The first catalyst bed
while the bottom walls are gas-impermeable. The first catalyst bed is in the outer basket
outer
and basketpart
the upper and theinner
of the upper part basket.
annular of the inner annular basket.

Figure 9. Reactor with the dual-bed catalytic system, forcing the gas to flow in the ax
Figure 9. Reactor with the dual-bed catalytic system, forcing the gas to flow in the axial–radial
direction:
direction: 1—perforated
1—perforated upperupper
wall of wall of the2—perforated
the basket, basket, 2—perforated side
side wall of the wall3—gas-
basket, of the baske
impermeable upper central wall of the basket, A—deNO
impermeable upper central wall of the basket, A—deNOx catalyst bed, B—deN2 O catalyst bed (based 2O cat
x catalyst bed, B—deN
(based
on patent on patent [88]).
[88]).

The second catalyst bed is in contact with the first catalytic bed through the perforated
side walls of the basket. However, in the upper part it is separated from the layer of the
first catalyst bed by a solid baffle/plate. The purified gas stream flows through the first
catalyst bed (deNOx ) in the axial and radial direction, while through the second catalyst
bed (deN2 O) only in the radial one. Then, it is collected in the central space of the reactor
and directed to its outlet. The reducing agent (ammonia or ammonia + hydrocarbon) is
mixed with the tail-gas stream before entering the first catalyst bed. The top layer of the
first catalyst acts as a sealing layer, preventing the gas stream from bypassing (in case of
settling of the catalyst bed, see Section 3.2) and simultaneously participates in the reaction.
This solution ensures a more even gas distribution over the catalyst bed, does not require
installing a heavy top cover plate in the upper part of the basket and using an excess
catalyst layer, which only serves as a sealing of the catalyst bed.
Mixed-flow reactors with axial and radial gas flow direction through the catalytic
baskets ensure lower operating and capital costs than those with two catalyst beds arranged
in annular baskets. It also allows for better use of the space inside the reactor (with the
same volume of available space inside the reactor, more catalyst can be installed in the
cylindrical basket compared to the annular one) and combines the advantages of the axial
and radial gas flow through the catalytic reactor. It is crucial for the catalysts, whose activity
under given process conditions depends to a greater extent on the amount of catalyst bed
(kinetic regime) than how the gas flows through it (linear gas flow velocity). The first
catalyst bed ensures at least partial flow of the gas stream in the axial direction and acts as
a layer protecting the catalyst bed against a gas bypassing. It occurs in the annular baskets
 Appl. Sci. 2023, 13, 7492 19 of 27

as a result of the catalyst bed settling. Hence, the catalyst bed is sealed in the upper part
using a top cover plate, whose side walls are even several centimetres wide. The weight
of such a construction is greater than that of the basket, forcing the gas flow in the axial
direction. Suppose a first catalyst bed, installed in the upper part of the reactor, forces the
gas flow in an axial direction. In that case, a lighter top cover plate can be used over a
second catalytic basket of annular shape (two catalyst beds arranged coaxially along the
reactor axis, spatially separated). The catalyst bed in the upper part of the reactor will
provide a smoother tail-gas inflow onto the second catalyst bed. In addition, a mixed gas
flow will be created within the second catalyst bed, including axial and radial velocity
components, which provide a better gas distribution over this bed. Installing one of the
catalyst beds in the annular catalytic baskets ensures a lower gas pressure drop than the
solution with two catalyst beds through which the gas flows in the axial direction. In the
case of the catalyst beds arrangement, in which the gas stream flows through the catalyst
beds first in the radial and then in the axial direction, back-mixing may occur. The bed
installed in the annular catalytic basket generates lower gas flow resistances in relation to
the bed in the cylindrical catalyst basket.
In the catalytic basket, by forcing gas flow in the axial direction, a catalyst with a higher
activity under given process conditions can be installed. This allows the use of shaped
catalyst bodies of a larger size, ensuring lower gas pressure drops across the catalyst bed. A
less active catalyst can be installed in a catalytic basket with an annular structure, in which,
due to the lower gas flow resistances, smaller catalyst bodies can be installed [35,88,92,93].

3.5. Lateral Flow Reactor

In the lateral flow reactor (LFR), as in the radial one, the gas flow direction through the
catalyst bed is perpendicular to the reactor axis. Therefore, it is characterized by a lower
linear gas flow velocity through the catalyst bed than the axial flow reactor. The catalytic
basket of the LFR reactor consists of a series of cassettes of small width, the side walls of
FOR PEER REVIEW 20 of 28
which are perforated, while the top and bottom parts are gas-impermeable (Figure 10). This
design allows only for installing one type of catalyst. Therefore, it is impossible to combine
the two catalytic processes, deNOx and deN2 O.

(a) (b)
Figure 10. (a,b) Lateral flow10.reactor
Figure (LFR):
(a,b) Lateral flow1—solid bottom
reactor (LFR): plate
1—solid of the
bottom basket,
plate of the 2—solid upper
basket, 2—solid partpart of
upper
of the basket, 3—perforated side
the basket, walls of the
3—perforated sidecassette, A—cassette
walls of the with a catalyst
cassette, A—cassette bed. bed.
with a catalyst

The tail-gas stream can be introduced in the top or bottom part of the reactor. It
initially flows in the axial direction into the space between the two catalyst beds. Then, it
hits the solid plate installed between the two cassettes in their upper part and flows
through their perforated side walls. After passing through the catalyst bed, the gas stream
Appl. Sci. 2023, 13, 7492 20 of 27

The tail-gas stream can be introduced in the top or bottom part of the reactor. It
initially flows in the axial direction into the space between the two catalyst beds. Then,
it hits the solid plate installed between the two cassettes in their upper part and flows
through their perforated side walls. After passing through the catalyst bed, the gas stream
exits the cassette through the second perforated wall and joins with the gas stream from
the adjacent cassette. The gas streams from the spaces between the cassettes merge and
leave the reactor through the outlet. The gas stream inside the cassette flows quite slowly,
which to some extent, limits the mass and heat exchange between the gas phase and the
catalyst surface. Therefore, LFR reactors are used for low-rate reactions, especially those
running mainly in the kinetic regime.
CFD calculations of the LFR reactors are performed to assess the reactor’s geometrical
parameters and the operating conditions impact on the hydrodynamic properties, i.e., gas
pressure drops across the catalyst bed or flow velocity distribution (transverse/lateral)
along the catalyst bed height. They are also used to estimate the friction factor against the
walls of the channels between the cassettes.
In LFR reactors, the pressure drop does not exceed 2 kPa. Typically, it is in the range
of 0.1–2.0 kPa at a gas flow rate of 2000–50,000 Nm3 /(m3 h), and cassette dimensions of
height × depth × width = (0.5 ÷ 2.0) × (0.5 ÷ 2.0) × (0.02 ÷ 0.1) m. A low pressure drop
(especially at a level of several hundred Pa) translates into a poorer gas distribution over
the catalyst bed, along the height of the cassette (uneven distribution of transverse/lateral
velocity). The uniformity of the gas flow through the LFR reactor can be improved by
using very small catalyst bodies or by increasing the width of the cassettes. However, this
translates into investment costs increase. The total pressure drop value is also affected by
the friction factor, which depends on the roughness of the channel walls [94–97].
Shell company offeres the LFR reactors as a Shell DeNOx system technology. Titania-
supported vanadium oxide catalysts in the form of trilobes, with dimensions 0.6–5.0 mm
(S-096), are installed in them.
The design of the LFR reactor ensures very low gas flow resistances across the catalyst
bed (lower than in the axial or radial flow reactor). Therefore, installing very small catalyst
bodies without the risk of excessive pressure drop value is possible. In this type of reactor,
high efficiency of the gas purification from nitrogen oxides is achieved, exceeding 95%
(Shell deNOx System, titania/vanadia catalyst). A particular problem is the uneven gas
distribution along the length of the cassettes. The construction of the catalytic basket is
quite complicated, as it consists of a series of perforated and solid plates, directing the flow
of the gas stream. Unloading and loading the catalyst into the cassette is also problematic
due to their large depth and small width. To better compact the catalyst bed in the cassette,
it is necessary for example to load it in batches and vibrate the bed. However, such a
procedure may contribute to catalyst crushing.

3.6. Parallel-Flow Reactor with Deflectors

A modification of the LFR reactor is the parallel-flow reactor with deflectors, shown
in Figure 11. Contrary to the solution in Section 3.5, the horizontal plates do not close the
channels between adjacent catalyst beds. The cassettes with the catalyst bed are connected
by deflectors fixed to the lower edge of one cassette and the upper edge of the other.
The diagonal plates (deflectors) between the cassettes ensure a smoother gas inflow
onto the catalyst bed, without generating significant turbulence in the gas flow. The resi-
dence time of the gas in the catalyst bed is also longer. At the cassette outlet, the deflectors
gently deflect the gas stream towards the reactor outlet. Probably, they also contribute to
reducing the friction factor (friction against the walls of channels) and declining the total
pressure drop compared to the classic LFR reactor. On the other hand, the presence of
deflectors makes the reactor design more complicated [98].
 However, such a procedure may contribute to catalyst crushing.

3.6. Parallel-Flow Reactor with Deflectors

A modification of the LFR reactor is the parallel-flow reactor with deflectors, shown
in Figure 11. Contrary to the solution in Section 3.5, the horizontal plates do not close the
Appl. Sci. 2023, 13, 7492 21 of 27
channels between adjacent catalyst beds. The cassettes with the catalyst bed are connected
by deflectors fixed to the lower edge of one cassette and the upper edge of the other.

(a) (b)

Figure
Figure 11. (a,b)Parallel-flow
11. (a,b) Parallel-flowreactor
reactorwith
withdeflectors
deflectors (based
(based onon Patent
Patent [98]):
[98]): 1—empty
1—empty cassette,
cassette, 2—
2—deflector, 3—perforated
deflector, 3—perforated sideside
wallwall of the
of the cassette,
cassette, 4—gas-impermeable
4—gas-impermeable top wall
top wall ofcassette,
of the the cassette,
A—
A—catalyst
catalyst bed.bed.

The diagonal plates (deflectors) between the cassettes ensure a smoother gas inflow
4. Conclusions
onto Table
the catalyst
1 presentsbed,
thewithout
advantagesgenerating significant of
and disadvantages turbulence in thedesign
the three main gas flow. The
solutions
residence time of the
of the catalytic baskets. gas in the catalyst bed is also longer. At the cassette outlet, the
deflectors gently deflect
An overview the gas
of the deNO stream towards the reactor outlet. Probably, they also
x /deN2 O catalytic reactors design used in nitric acid plants,
as well as the types of catalysts usedfactor
contribute to reducing the friction in NO(friction against the walls of channels) and
x and N2 O reduction (NOx reduction—TiO2 -
declining the total pressure drop compared to the classic
supported vanadium oxide, NOx and N2 O reduction—iron-modified LFR reactor. zeolites)
On the other hand,
and direct
the presence of deflectors makes the reactor design more complicated [98].
N2 O decomposition (iron-modified zeolites, zinc-cobalt spinel) were presented. Before
installing in the reactor, the catalyst should be appropriately shaped. The catalyst shaped
4. Conclusions
body affects the size of the geometric surface available for the reactants, mass and heat
transfer between
Table thethe
1 presents catalyst surface
advantages and
and the gas phase,
disadvantages as three
of the well as thedesign
main pressure drop.
solutions
Catalysts in the form
of the catalytic baskets. of spheres, extrudates, trillobes and monoliths are often used in nitric
acid plants in deNOx /deN2 O reactors.
TableThe
1. Advantages
efficiency ofand disadvantages
tail-gases of the catalytic
purification basket design
from nitrogen oxidesinis deNO x/deN
affected 2Oonly
not reactors.
by the
type and shape of the catalyst, but also by the method of its installation inside the reactor
The Direction of a Gas
(design of the catalytic basket). Various aspects of designing deNOx /deN2 O reactors were
Flow through the Advantages
described, including modelling their operation using CFD Disadvantages
calculations. Several types
Catalyst Bed of reactors that can be used in nitric acid plants, differing in how the gas stream flows
 through
Simple design
the catalyst bed, were presented.  Three
High gas flow
main resistances
types of reactors, which are the
axial  basis
Easyfor
loading
otherand unloading
design  radial
solutions, are axial, Increasing the volume
and lateral of the catalyst
flow reactors. bedcase,
In the first
of the catalyst requires increasing the reactor diameter—a
the gas stream flows through the catalyst bed in a direction parallel to the reactor axis,
and the catalytic basket is often cylindrical. In the radial and lateral flow reactor, the gas
stream flows in a direction perpendicular to the reactor axis and the catalytic basket has an
annular shape or rectangular cassettes, respectively. The lowest gas flow resistances and
the highest efficiency in tail-gas purification from nitrogen oxides (in the case of catalyst in
the form of grains) are provided by the lateral flow reactor. The limitation is the inability
to integrate catalysts for deNOx and deN2 O processes inside one reactor. For the proper
operation of the lateral reactor, it is necessary to ensure an even gas distribution over
the catalyst bed, along the height of the cassettes. The deflectors can be installed in the
channels between the cassettes to: ensure a smoother gas inflow onto the catalyst bed,
extend the gas flow path before it enters the catalyst bed, improve gas distribution over the
bed along the height of the catalytic basket or reduce the total gas flow resistances through
Appl. Sci. 2023, 13, 7492 22 of 27

the reactor. However, this makes basket construction more complicated and problematic
in the case of maintenance works. The deNOx and deN2 O catalyst beds can be arranged
in the reactor along the diameter of the reactor and its axis, in the cylindrical or annular
catalytic baskets. Combining the axial and radial flow inside one reactor makes it possible
to use the advantages of both design solutions (see Table 1).

Table 1. Advantages and disadvantages of the catalytic basket design in deNOx /deN2 O reactors.

The Direction of a
Gas Flow through the Advantages Disadvantages
Catalyst Bed
4 Simple design 4 High gas flow resistances
4 Easy loading and unloading of the catalyst 4 Increasing the volume of the catalyst bed
axial 4 More efficient use of the available space requires increasing the reactor diameter—a
inside the reactor—the possibility of thicker and more expensive reactor shell
installing a larger volume of the catalyst bed undergoing faster exploitation

4 More complex and expensive catalytic basket

4 Low gas flow resistances
4 Low linear gas flow velocity through the
catalyst bed
4 High efficiency of tail-gases purification from
nitrogen oxides
4 Possibility of using smaller catalyst shaped
radial bodies without the risk of excessive pressure
drop increase
4 Possibility of varying the gas flow resistance
through the catalyst bed along the height of
the catalytic basket (by using different holes
sizes and varying their location on the
perforated side walls of the basket)
design
4 The presence of a heavy top cover plate in
the upper part of the catalytic basket
4 A larger catalyst bed volume by 5–20% is
required, acting as a sealing layer, protecting
the basket against gas bypassing
4 More problematic loading and unloading of
the catalyst (including installing and
uninstalling a top cover plate)
4 Problem with uniform gas distribution over
the catalyst bed along the height of the
catalytic basket
4 Settling of the catalyst bed—a risk of gas
bypassing

4 Very low gas flow resistances 4 Complex design, problematic in maintenance

4 Low linear gas flow velocity through the
catalyst bed
4 The LFR reactor can be used in case of low
gas flow rates—“end-of-pipe” location
lateral
4 Very high efficiency of tail-gas purification
from nitrogen oxides
4 Possibility of using small catalyst shaped
bodies
works
4 With the same volume of available space
inside the reactor compared to the axial and
radial reactors, it is possible to install the
smallest volume of the catalyst
4 Problem with uniform gas distribution over
the catalyst bed, along the height of the
cassettes
4 Problematic catalyst loading and unloading

Author Contributions: Conceptualization, P.C., M.R., M.I., M.W. and A.R.; Writing—original draft
preparation, P.C. and M.R.; writing—review and editing, P.C., M.R., M.I., M.W. and A.R.; Supervision,
M.R., M.W., M.I., A.R.; Investigations, P.C., M.I. and M.R. All authors have read and agreed to the
published version of the manuscript.
Funding: P.C. acknowledge the financial support founded by the program of the Ministry of Science
and Higher Education entitled “Implementation Doctorate”.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
Appl. Sci. 2023, 13, 7492 23 of 27

Abbreviations
Symbols
µ viscosity of the gas flowing through the catalyst bed [Pa·s]
ε bed voidage [m3 ]
ρf density of the gas flowing through the catalyst bed [kg/m3 ]
ρw density of the shaped catalyst body [kg/m3 ]
mw mass of the shaped catalyst body [kg]
x spherical equivalent particle diameter [m]
A Blake–Kozeny–Carman coefficient
B Plummer coefficient
H height of the catalyst bed [m]
∆P pressure drop across the catalyst bed [Pa]
Si surface of the catalyst body [m2 ]
V linear gas flow velocity [m/s]
Vi volume of the shaped catalyst body [m3 ]
Vtot total volume of the catalyst bed [m3 ]

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