Article

Cite This: Ind. Eng. Chem. Res. 2019, 58, 19406−19420 pubs.acs.org/IECR

Dynamic Carbon Dioxide Methanation in a Wall-Cooled Fixed Bed

Reactor: Comparative Evaluation of Reactor Models
Konrad L. Fischer, Moritz R. Langer, and Hannsjörg Freund*
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Lehrstuhl für Chemische Reaktionstechnik, Cauerstr. 3, 91058
Erlangen, Germany
*
S Supporting Information

ABSTRACT: A comprehensive model comparison is presented for

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the description of the steady state and dynamic behavior of a wall-

cooled fixed bed methanation reactor. First, the maximal conversion
predicted by different steady state models is compared and evaluated.
Second, the dynamic reactor behavior is investigated based on
positive and negative step changes of the inlet flow rate. The
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examined model complexity ranges from a simple one-dimensional

pseudohomogeneous reactor model to a two-dimensional heteroge-
neous model. The results show that similar maximal conversions are
predicted by each model, but large discrepancies appear for the
prediction of the dynamic reactor behavior. Our data clarify the
impact of the considered heat and mass transfer resistances on the
model prediction and allow us to give specific recommendations for further steady state and dynamic modeling works.

1. INTRODUCTION
The methanation of carbon oxides gained renewed interest as a
power-to-gas concept for energy storage.1−13 Excess electricity
is used to produce hydrogen by the electrolysis of water. Then,
hydrogen is converted to methane by the addition of carbon
oxides. The dried product gas mixture consists of methane,
unconverted hydrogen, and carbon oxides and is called
synthetic natural gas (SNG), which can easily be stored and
distributed by existing infrastructure if the requirements of the
gas quality are met. A power-to-gas plant can be located in a
decentralized manner, close to the power or carbon oxide
source, in order to minimize the distribution effort. However,
due to the volatile nature of excess electricity, also the
electrolyzer produces fluctuating quantities of hydrogen.
Therefore, a steady state operation of the methanation reactor
can only be maintained by large storage facilities of hydrogen
and carbon oxides in order to buffer the fluctuating supply. In
particular, hydrogen storage is expensive, which influences the
investment costs of the power-to-gas plant.1 The size of storage
facilities can be reduced by a dynamic operation of the
methanation reactor, which follows the hydrogen production.
However, designing an efficient methanation reactor for the
dynamic operation is a difficult task due to the strong
exothermicity of the reaction as well as possible dynamic
influences of a load change. Therefore, systematic model-based
design approaches are necessary. In this context, the choice of
an adequate reactor model is a primary step which decisively
determines the applicability and reliability of the resulting
design.
The methanation process is established with different
reactor concepts but mostly for the coal-to-SNG process. We
here keep the technolgoy review brief and refer to the detailed
reviews of Rönsch et al.2 and Kopyscinski et al.14 Most
concepts are multiple adiabatic fixed bed reactors in series with
intermediate gas cooling. Also, fluidized-bed reactors and
three-phase reactors are investigated. Cooled fixed bed reactors
have gained much research interest since they allow for a better
temperature control and a reduction of reactor stages. In line
with that, a focus of recent numerical works is the dynamically
operated methanation in both adiabatic and cooled fixed bed
reactors.1−13
The numerical investigation of fixed bed reactors and their
dynamic operation requires reliable mathematical models. The
reactor models can be distinguished regarding dimensionality
and phase treatment. Heterogeneous models describe the gas
and catalyst phase separately. The model considers heat and
mass transfer resistances between the phases and within the
catalyst pellet. Pseudohomogeneous models neglect these
transport resistances, and therefore, fluid and catalyst phase
can be aggregated to one phase. Two-dimensional models
describe gradients in axial and radial directions, whereas one-
dimensional models neglect radial gradients.
Numerous numerical studies have been published reporting
progress in the design and operation of the unsteady-state
methanation of carbon oxides in fixed bed reactors.3−13 A
common approach is the investigation of the reactor dynamics
by varying one or more inlet conditions and then examining
Received: May 26, 2019
Revised: September 9, 2019
Accepted: September 23, 2019
Published: September 23, 2019

© 2019 American Chemical Society 19406 DOI: 10.1021/acs.iecr.9b02863

Ind. Eng. Chem. Res. 2019, 58, 19406−19420
Industrial & Engineering Chemistry Research Article

the reactor response. In doing so, the studies differ in the
chosen reactor setup (e.g., reactor dimensions, number of
stages, recycle) and the varied inlet conditions. Moreover, the
level of complexity regarding the chosen models differs. Most
recently, Kreitz et al.3 published results on the periodic
operation of a microstructured fixed bed reactor using a one-
dimensional heterogeneous model. A periodically varying feed
composition causes considerable changes in the hot-spot
temperature and its position and also reduces the product gas
quality.3 Matthischke et al.5 investigated the start-up time of
both an adiabatic and cooled fixed bed reactor. The reactor is
described by a one-dimensional pseudohomogeneous mass
balance, a heterogeneous energy balance with isothermal pellet
temerpature, and a separate energy balance of the reactor wall.
The authors conclude that the start-up time is influenced by
the different heat storage capacities in the system and the
superficial gas velocity. The scenario of a shut-down and restart
of an insulated fixed bed reactor was discussed by Rönsch et
al.6 using a two-dimensional pseudohomogeneous model
neglecting radial mass transport. Regarding the reactor start-
up, Bremer et al.7 optimized the start-up process by controlling
the coolant temperature. Here, a two-dimensional pseudoho-
mogeneous model was used. A comprehensive work was
published by Try et al.,9 where a two-dimensional heteroge-
neous reactor model was used to describe both the dynamic
variations of the load and the inlet temperature. Those changes
provoke moving hot spots and a wrong-way behavior.
Without a claim of completeness, the summary of recent
publications shows a large spectrum of dynamic reactor models
with considerable different levels of complexities although the
addressed research interests are closely related. That spectrum
of used models makes a comparison and evaluation of the
published results difficult.
A detailed comparison of different dynamic reactor models
and their effect on the predicted reactor operation is currently
missing for the methanation literature. Therefore, it is the goal
of the present work to provide deeper insights into the
adequate model selection for the numerical simulation of the
dynamic reactor operation for the methanation of carbon
recommendations for further works are summarized in section
5.
2. MATHEMATICAL MODELS
In the present work, we use a total of eight reactor models to
describe the steady state and dynamic temperature and
concentration profiles in a wall-cooled fixed bed methanation
reactor. The models differ in their dimensionality and phase
treatment. In this section, we introduce the reactor models
which include balance equations, the reaction kinetic model,
correlations, and physical property methods.
2.1. Balance Equations. The basis of the model
comparison is models with successively increased complexity.
The extent of the model comparison is limited by some general
simplifications. Frequently, high superficial velocities are
reported for the methanation in fixed bed reactors.5,7,13 In
this case, axial mass and energy transport based on dispersion
or conduction, respectively, is small compared to the
convective transport.
In this work, the velocity field is described by simple plug-
flow conditions. The model precision can further be increased
by the consideration of the radial velocity profile and
integration of the extended Brinkmann equation and the
radial porosity profile, which is especially relevant for low tube-
to-particle diameter ratios. However, the impact of this model
extension on the model prediction is not part of this work.
Thermal conduction, radial dispersion, and diffusion in the
spherical pellets are described by Fourier’s and Fick’s
approach, respectively. The balance equations are derived for
gas, catalyst, and coolant.
Heterogeneous Model. On the basis of the given
assumptions, the most complex model in our work is a
dynamic two-dimensional heterogeneous reactor model with
separate balance equations of the gas phase (G) and catalyst
pellet phase (P). The gas phase balance equations account for
the accumulation of mass and heat, radial mass dispersion and
effective radial heat transport, axial convective transport of
mass and heat, and their exchange with the catalyst pellet. The
mass and energy balance equations are given as follows:

1 ∂ ijj ∂wG yz
jjrDα , r α zzz − vz α
oxides. The interesting question that arises is to what extent

r ∂r jk ∂r z{
the simplifications usually applied for a steady state problem ∂wαG ∂wG
εbed =
are suitable for a dynamic problem as well. ∂t ∂z
In this contribution, we perform a detailed model
comparison for a wall-cooled fixed bed methanation reactor. β GP
+ Sv(ραP − ραG )
A total of eight reactor models, which include four steady state ρ̅ G y = d /2 (1)
and four dynamic models of different levels of complexity, are
1 ∂ ijj eff ∂T G yzz
jjjrλr zzz − vzρ ̅ G c p̅ G
presented. The model complexity ranges from a simple steady
∂T G ∂T G
r ∂r k ∂r {
state one-dimensional pseudohomogeneous model to a ρ ̅ G c p̅ Gεbed =
dynamic two-dimensional heterogeneous model. At first, the ∂t ∂z
steady state operation of a methanation reactor with fixed tube
and particle dimensions is compared. Then, dynamic, step + αGPSv(T P − T G)
y = d /2 (2)
change simulations of the flow rate are performed, and the
discrepancies between the model predictions are captured. Within the pellet it is most commonly not further
This approach allows the dominating influences to be revealed distinguished between a solid and gaseous phase, but the
on both steady state and dynamic model prediction in order to conditions are aggregated to one pseudohomogeneous pellet
support further modeling works. phase. The balance equations of the pellet phase consider the
The remainder of the manuscript is structured as follows. In accumulation of mass and heat, their transport based on
section 2, we introduce the considered reactor models and the diffusion and conduction, and the chemical reaction:

1 ∂ ijjj 2 ∂ραP yzz

methanation reaction in more detail. In section 3, the

j α ,y zz + Mαρcat
y 2 ∂y jjk ∂y zz
methodology of the model comparison is presented. The ∂ραP nR

{
results of the steady state and dynamic model comparison are εcat = y D ∑ να ,iri
∂t (3)
discussed in section 4. At last, the conclusions and i=1

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1 ∂ ji ∂T P zyz
= 2 jjjy 2 λcat z + ρcat
y ∂y jk ∂y zz{
nR
∂T P ∂wα ∂wα
ρcat c p,cat ∑ ΔHR,iri wα|z = 0 = wα ,in ,
∂r
= 0,
∂r
= 0,
∂t i=1 (4) r=0 r=R

The catalyst density is given as pellet mass per pellet volume: ∂T

T |z = 0 = Tin , = 0,
ρcat = (1 − εcat)ρs. Also, the heat capacity of the gas within the ∂r r=0
pellet is negligible in comparison to the solid phase heat
capacity. ∂T αw
= eff
(Tc − T r = R )
Pseudohomogeneous Model. The second type of reactor ∂r r=R λr r = R (11)
models we use in the present work are pseudohomogeneous
reactor models, which are popular in the methanation The boundary conditions of the pellet for all t in (0, tf] are
literature.5−7,13 Here, the properties of gas and catalyst phases
are described as one pseudohomogeneous phase where the ∂ραP ∂ραP β GP
heat and mass transfer resistances between the phases and = 0, = (ραG − ραP ),
∂y ∂y Dα y = d /2
within the pellet are neglected. Therefore, the model y=0 y = d /2
y=R p
complexity is considerably lower in comparison to heteroge-
neous models. The pseudohomogeneous mass and energy ∂T P ∂T P αwGP G
balance equations are given as follows: = 0, = (T − T P )
1 ∂ ij ∂w y
jjrDα , r α zzz − vz α
∂y ∂y λcat y = d /2
y=0 y = d /2

r ∂r k ∂r {
∂w ∂w
εbed α = (12)
∂t ∂z
The boundary condition of the coolant balance for all t in (0,
Mα(1 − εbed)ρcat nR tf] is
+ ∑ να ,iri
ρ̅ i=1 (5) Tc z = 0 (t ) = Tc,in(t ) (13)
∂T Initial Conditions. Dynamic reactor models require also
[ρ ̅ c p̅ εbed + ρcat c p,cat(1 − εbed)]
1 ∂ ij eff ∂T yz
∂t initial conditions of the states which are given for z in [0, L]
jjrλr zz − vzρ ̅ c p̅
r ∂r k ∂r {
∂T and r in [0, D/2]:
=
∂z
nR ραG (t = 0, z , r ) = ραG,0 , ραP (t = 0, z , r , y) = ραP,0 ,
+ (1 − εbed)ρcat ∑ ΔHR, iri
T G(t = 0, z , r ) = T0G , T P(t = 0, z , r , y) = T0P ,
i=1 (6)
The accumulation of energy accounts for the different heat Tc(t = 0, z) = Tc,0 (14)
storage capacities of the gas and catalyst phase.
Total Mass Balance. For all models, the plug-flow velocity Simplified Model Derivatives. In our work, also simplified
field is calculated based on the total mass balance: reactor models are used for the detailed model comparison.
They can be derived from the above given balances. In order to
ρin̅ G (t ) describe a reactor at the steady state, the accumulation term on
vz(z , t ) = vz ,in(t ) the left side of the balance equations is eliminated. One-
ρ ̅ G (z , t ) (7) dimensional formulations are derived by integration in the
Coolant Balance. The focus of this work is models of the radial direction and inserting the respective boundary
reactor fixed-bed packing. The coolant (c) side is important conditions. Both the heterogeneous and pseudohomogeneous
regarding the heat removal but, here, described with less detail. balance equations are simplified to the one-dimensional
Furthermore, the energy balance of the wall is not considered formulation. The pellet balances are not further simplified.
here, which can also impact the overall dynamic behavior of a All model derivatives are given in the Supporting Information
reactor as discussed by Matthischke et al.5 The simple one- of this work.
dimensional energy balance with constant fluid properties and 2.2. Reaction Kinetic Model. The methanation of carbon
velocity is given as follows: dioxide is an exothermic equilibrium reaction with volume
reduction. The reaction can be described by a direct carbon
∂Tc ∂T πD dioxide methanation in a single step:15
ρc c p,c = −ρc c p,cvc c + αw(T − Tc)
∂t ∂z Ac (8)
CO2 + 4H 2 F CH4 + 2H 2O ΔHR0 = −165 kJ/mol
If the coolant parameters are not of some specific importance, (15)
they can be aggregated to one parameter, Kc. 2
In a recent review, Rönsch et al. summarize that the kinetic
∂Tc ∂T models of Xu and Froment16 and Kopyscinski17 were most
= −vc c + Kcvcαw(T − Tc)
∂t ∂z (9) frequently used for methanation modeling and simulation
studies so far. However, the more recent model of the carbon
πD dioxide methanation by Koschany et al.15 has gained attention
Kc =
Acρc c p,cvc (10) and is used in the latest research.3,5,13 The investigated catalyst
shows high activity at relatively mild temperatures, where the
Boundary Conditions. The boundary conditions of the carbon monoxide formation via the water−gas shift reaction is
pseudohomogeneous phase or the gas phase of the negligible. The rate is described by a Langmuir−Hinshel-
heterogeneous model are given for all t in (0, tf]: wood−Hougen−Watson (LHHW) approach:
19408 DOI: 10.1021/acs.iecr.9b02863
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Industrial & Engineering Chemistry Research Article

0.5 i
jj1 − zyz
2j
j zz
pCH pH2 O where λbed is the conductivity of the fixed bed without fluid
k {
k·pH0.5 pCO 4 2
pCO pH4 K eq flow. Pe0 is the particle Peclet number and Kr is a correction

ij y
2

jj1 + K OH H0.52O + K H p 0.5 + K mixp 0.5 zzz

2 2
r= term. Test simulations within our work showed that the

j CO2 z
2

k {
p influence of radiation is negligible in the investigated
pH
2
2 H2
(16)
The parameters were determined for temperatures between
453.15 and 613.15 K and pressures between 5 and 15 bar. We
refer to ref 15 for more details about the model derivation and
the parameter values.
The kinetic model describes the reaction rate for steady state
conditions. Frequently, kinetic models based on steady state
experiments are also used for dynamic simulations3,5,7−9 due to
a lack of kinetic models, which also incorporate dynamic effects
on the catalyst surface. The usage of kinetic models based on
steady state experiments for dynamic reactor models is a
limitation of both previous dynamic simulations studies and
our work. It is a current topic of research to develop kinetic
models for a more precise description of dynamic processes.
2.3. Correlations and Physical Property Methods. The
reactor model is completed by correlations and property data
of the components. The pressure drop is calculated based on a
correlation instead of the momentum balance. An exothermic
reaction and especially the methanation is commonly operated
in reactors with a low tube-to-particle diameter ratio.
Therefore, we used the correlation of Eisfeld and Schnitzlein,18
which accounts for the wall effect in finite packings:
temperature range. More details on the correlation can be
found in the given references. The precision of the overall heat
transfer coefficient to the coolant can further be improved by
the consideration of the thermal resistance of the tube wall and
the resistance at the outer tube wall to the coolant. For small
wall thicknesses with high thermal conductivity and appro-
priate properties of the coolant flow, these resistances are small
in comparison to the resistance at the inner tube wall. For
reasons of simplicity, we here neglect these additional
resistances.
Radial dispersion of mass is calculated according to Tsotsas
and Schlünder:25
vzd
Dr , α = (1 − 1 − εbed )δα ,m +
8 (22)
The component diffusion coefficients in the gas mixture δα,m
are calculated based on the mixing rule of Fairbanks and
Wilke26 and the binary diffusion coefficients according to
Fuller et al.27 For the effective diffusion coefficients within the
pellet, the pellet porosity εcat and its tortuosity τ are
considered:
ε

ij A w 1 − εbed ρ ̅ vz2 yzz

Dα , y = cat δα ,m

= −jjj154A w2 zz
τ (23)

j d z{
dp (1 − εbed)2 η ̅ vz
k
3
+ The component specific mass transfer between the gas and
dz εbed d2 Bw εbed3
pellet phases is calculated on the basis of the Sherwood
(17) numbers Shα = βGP
α d/δα,m according to Wakao and Funazkri:
28

The wall correction terms are given as

Shα = 2 + 1.1Scα1/3Re00.6 (24)
2
Aw = 1 + , where the Schmidt numbers are defined as Scα = η̅G/ ρ̅Gδα,m.

ÄÅ ÉÑ2
3(D/d)(1 − εbed)
ÅÅ ÑÑ
Gnielinski29 suggests a correlation for the heat transfer
ij d yz
Å
Bw = ÅÅ1.15jj zz + 0.87ÑÑÑÑ
Å
between the gas and pellet phases on the basis of the Nusselt
ÅÅ ÑÑ
2

ÅÇ kD{ ÑÖ
number of a single particle Nu = αGPd/λ̅G:
(18) Nu = (1 + 1.5(1 − εbed))Nusphere (25)
The heat transport coefficient at the wall αw for the two-
dimensional reactor models is calculated based on the Nusselt 2 2
Nusphere = 2 + Nulam + Nuturb (26)
number Nuw = αwd/λ̅G. Martin and Nilles19 suggest a

i 5 yz λbed
correlation for Nuw as follows:

Nu w = jjjj1.3 +
Nulam = 0.664 Reε 3 Pr
zz
(27)

k D/d z{ λG
+ 0.19Re00.75Pr 0.33 0.037Reε0.8Pr
(19) Nuturb =
1 + 2.443Reε−0.1(Pr 2/3 − 1) (28)
where Re0 is the particle Reynolds number and Pr the Prandtl
number. For one-dimensional models, we follow the vzdρG̅
suggestion of Dixon20 to describe the heat transport at the Reε =
wall by an overall heat transfer coefficient kw which takes the ηG̅ εbed (29)
thermal resistance of the catalyst bed into account: The specific molar heat capacities, enthalpy of formation, and
1 1 D Bi + 3 molar entropy of the gaseous components are calcualted on the
= + basis of the Schomate equation and data from the NIST
kw αw 6λreff Bi + 4 (20)
Chemistry WebBook.30,31 The components’ thermal con-
where the tube Biot number is Bi = αwD/2λeff
r .
The effective ductivities and dynamic viscosities are calculated according
radial conductivity λreff is calculated according to the to Kleiber and Joh.32 The thermal conductivity and dynamic
correlations of Zehner and Schlünder21 and Bauer22,23 (also viscosity of the gas mixture are calculated according to the
summerized by Tsotsas24). It consists of a static and convective mixing rules of Wassiljewa33 and Wilke,34 respectively. The
part: ideal gas law is applied as an equation of state.
Pe0 2.4. Numerical Solution Strategy. The given balance
λreff = λbed + λG̅ equations and the correlation for the pressure drop result in a
Kr (21) system of partial differential equations (PDEs) and ordinary
19409 DOI: 10.1021/acs.iecr.9b02863
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Industrial & Engineering Chemistry Research Article

differential equations (ODEs). The PDEs are reduced to a Table 1. Model Parameters of the Wall-Cooled Fixed Bed
system of ODEs by the Finite Volume Method (FVM). First Methanation Reactor (Single Tube)
order spatial derivatives are discretized by the upwind
parameter unit value
differencing method and second order derivatives by the
central differencing method. Remaining ODEs (temporal reactor
derivative) are solved by orthogonal collocation on finite L m 3.43
elements with third order orthogonal polynomials. The chosen D m 0.01
disretization approach showed a good convergence behavior of ntot,in mol/s 3.85 × 10−2
the performed optimization and simulation tasks. The
equations are implemented in the algebraic modeling language catalyst
AMPL35 and solved with Ipopt.36 A good trade-off between d m 0.002
model precision and computation time was found for 50 λcat W/Km 0.15
equidistant axial elements and 10 nonequidistant radial cp,cat J/kgK 1100
elements with coextensive volume. Regarding the heteroge- ρcat kg/m3 2300
neous reactor models, for each control volume, the balance εcat 0.4
equations of a representative catalyst pellet are solved. The τcat 4
pellet was discretized in 10 nonequidistant elements with
coextensive volume. By implementing a nonequidistant mesh, coolant
the precision can be increased in comparison to the equidistant ρc kg/m3 1680
grid with the same number of elements. Regarding dynamic cp,c J/kgK 1560
simulations, a step change in the flow rate provokes large Ac m2 2.3 × 10−5
gradients within the first physical seconds. Moreover,
simulations of longer time periods require a large number of
Koschany et al.15 The coolant density and heat capacity
discrete elements. This can lead to long computation times and
represent a molten salt cooling. The cross-sectional area used
also memory problems of the used hardware. That problem is
for the coolant balance is chosen in a way that the coolant
overcome by a sequential simulation approach of smaller time
velocity is in the range of 1 to 1.5 m/s, which is in the range of
steps. The time scale is cut in a number of elements which are
the gas velocity. This is also in line with recommendations for
solved consecutively. At each time step, the initial conditions of
the design of multitubular heat exchangers.37 We observed that
the ODEs are updated to the final values of the previous step.
a lower coolant velocity can cause undesired influences on the
dynamic reactor behavior which are not the objective of our
3. METHODOLOGY
study. Alternatively, boiling water could be used as the coolant,
The main aim of this work is to identify the influence of and the temperature could be assumed as constant. However,
transport resistances on the steady state and dynamic model here, we follow the design suggestion of El Sibai et al.13
prediction by means of a model comparison. Concentration 3.2. Comparative Evaluation of Reactor Models. In
and temperature profiles within a wall-cooled fixed bed reactor our work, we introduce an approach for a consistent steady
are calculated over time and compared for different models. state and dynamic reactor model comparison. The approach of
The model comparison is performed for a reactor with fixed the steady state model comparison is to compare the optimal
dimensions, i.e., reactor diameter, length, and catalyst pellet reactor performance predicted by different models. In this
size. In this section, we present the reactor design and the scenario, the inlet molar flow rate ṅtot,in is fixed, but the control
methodology of the model comparison. variables (Tin, Tc,in, Kc, pin) are degrees of freedom for each
3.1. Reactor Design. We consider the choice of an model. The feed consists of hydrogen and carbon dioxide in
appropriate reactor design as an important part of a meaningful the stoichiometric ratio at all times. Now, in order to predict
model comparison. For example, an oversized reactor which the optimal reactor performance with different models, an
operates at the equilibrium will not allow for a reasonable optimization problem is solved where the control variables are
evaluation of dynamic conversion changes. Also, design varied in order to maximize the carbon dioxide conversion:
parameters such as tube and particle diameter are of crucial
importance for reactions with high exothermicity. In order to max XCO2
DoF
avoid an experience based reactor design approach, we derived
an appropriate reactor design similar to the design of El Sibai DoF = {Tin , Tc,in , Kc , pin } (OP 1)
et al. using model based reactor optimization.13 For the
s.t.
optimization, we used our 1D pseudohomogeneous steady
state reactor model and slightly modified design constraints in • Model equations,
comparison to El Sibai et al.13 Details on the derivation of the • Reactor dimensions and inlet molar flow rate,
reactor design can be found in the Supporting Information. • Coolant constraint, bounds.
The parameter values of the reactor design including length, The optimization of the conversion is constrained by the
tube diameter, particle diameter, and total inlet molar flow rate reactor model, the reactor size, molar flow rate, and bounds of
are given in Table 1. Due to the high exothermicity of the the kinetic model. Furthermore, the temperature control of the
methanation reaction, the reactor has a low tube-to-particle reactor is most important. The formation of a distinct hot spot
diameter ratio. The remaining parameter values of the reactor can lead to severe safety issues especially for unsteady operated
model are taken from the literature or are assumed values. reactors due to the very high sensitivity to fluctuations. In their
Catalyst porosity, tortuosity, and heat capacity are assumptions detailed study of periodic fluctuations in the feed composition,
and chosen in line with previous works.3,5,6 Density and Kreitz et al. show that the hot spot temperature is extremely
thermal conductivity of the catalyst pellet are approximated by sensitive even for low amplitudes (change of inlet mole
19410 DOI: 10.1021/acs.iecr.9b02863
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Industrial & Engineering Chemistry Research Article

fractions).3 Kreitz et al. report temperature deviations well solution. Therefore, this rather low threshold was identified as
above 100 K.3 This can lead to severe material stress, catalyst a useful value to allow for a comparison of the simulation
deactivation, and also large fluctuations in conversion and results.
methane selectivity. In this work, we introduce a constraint As a result of the dynamic simulations, the time until an
that limits the temperature difference between the coolant and event is reached can be compared for different models.
reactor to 20 K in the steady state. While this approach Furthermore, it can be investigated whether different models
strongly limits the temperature in the reactor to rather mild predict the same event or not, i.e., one model predicts a new
conditions, it allows a better temperature control and inhibits steady state and the other model a runaway.
the formation of a distinct hotspot.
A consistent formulation of the temperature constraint 4. RESULTS AND DISCUSSION
between the reactor and coolant is necessary regarding the The first part of the results deals with the comparison of steady
different models. For the heterogeneous models, the difference state reactor models. It is investigated how the chosen model
between the gas phase and coolant is used, and for the two- complexity impacts the optimal reactor configuration. Then,
dimensional models, the temperature is averaged over the the key influences on the model prediction are extracted with a
radial coordinate to calculate the difference: focus on the considered heat and mass transport resistances. In
1D Hom: |T (z) − Tc(z)| ≤ 20K (30)
the second part of the results, the dynamic models are
compared. The optimized steady state operation point is
1D Het: |T G(z) − Tc(z)| ≤ 20K disturbed by a step change of the inlet molar flow rate. We
(31)
discuss differences of the time until a new steady state is
2D Hom: |T̅ (z) − Tc(z)| ≤ 20K reached or a reactor runaway occurs.
(32)
4.1. Comparison of Steady State Reactor Models. For
2D Het: |T̅ G(z) − Tc(z)| ≤ 20K the steady state model comparison, the operation conditions of
(33)
the wall-cooled reactor with fixed dimensions are optimized for
As a result of the optimization problem, the optimal steady each model according to the presented optimization method-
state conversion as well as temperature and concentration ology (see section 3.2). Multiple reactor load scenarios are
profiles predicted by the different models can be compared. An considered. The first case is a high reactor load with ṅtot,in =
alternative approach for the model comparison is forward 3.85 × 10−2 mol/s (vz,in ≈ 1.4 m/s); the second case is a lower
simulations of each model based on the same operation load with ṅtot,in = 2.31 × 10−2 mol/s (vz,in ≈ 0.8 m/s). The
conditions. However, this approach has some distinct optimization problem OP 1 is solved for each load scenario for
disadvantages for both the steady state and dynamic model four models: (1) a one-dimensional pseudohomogeneous
comparison. We refer to the Supporting Information for a model, (2) a two-dimensional pseudohomogeneous model,
more detailed discussion about the comparison methodology. (3) a one-dimensional heterogeneous model, and (4) a two-
The evaluation of different dynamic reactor models is based dimensional heterogeneous model.
on the optimized steady state operation points. In our dynamic The overall result is that the maximal conversion predicted
scenario, at first, the reactor is operated at the calculated steady by each of the models is in a close range. The deviation is less
state operation point which is characterized by the inlet molar than three percentage points (see Table 2). Both two-
flow rate and optimal inlet temperature, pressure, and coolant dimensional models describe slightly higher conversions than
flow rate and temperature. Then, the operation point is
disturbed by a step-change of the inlet molar flow rate Δṅin. Table 2. Optimal Reactor Conditions Calculated with
The other operation conditions are kept constant. This Different Reactor Models for Two Load Scenariosa
scenario is chosen in the context of a power-to-gas process
DOF unit 1D Hom. 2D Hom. 1D Het. 2D Het.
where the inlet molar flow rate varies due to a fluctuating
hydrogen production. Furthermore, this scenario is interesting case 1 ntot,in = 3.85 × 10−2 mol/s (100%)
since a change of the inlet flow rate strongly affects the heat Tin K 514.5 515.7 509.4 511.0
transport in the reactor. Tc,in K 494.2 494.6 489.1 489.4
The step change of the flow rate has two possible outcomes. pin bar 15 15 15 15
Either a new steady state is reached or an unstable state, i.e., a Kc Km/kW 0.35 0.35 0.40 0.39
runaway behavior, develops. Each simulation scenario is
performed for all dynamic models. As a measure for the performance
model comparison, the time from disturbance to the steady XCO2 84.9% 85.5% 82.0% 82.2%
3
state or runaway is recorded. The time when either of the cases STY mol/m s 24.3 24.4 23.4 23.5
is reached is identified using a threshold regarding the
temperature change in the reactor: case 2 ntot,in = 2.31 × 10−2 mol/s (60%)
Tin K 504.8 506.2 501.3 503.1
steady state: 0.001 K > max T (z , i) − T (z , i − 1)) (34) Tc,in K 484.4 484.9 480.9 481.2
pin bar 15 15 15 15
runaway: 550 K > max T (z , i) (35)
Kc Km/kW 0.52 0.52 0.55 0.53
where the index i represents the discrete time. For the
heterogeneous models, the gas phase temperature was performance
considered. Our simulation results showed that when temper- XCO2 88.7% 88.9% 86.3% 86.1%
atures in the range of the given runaway threshold were STY mol/m s 3
15.2 15.2 14.8 14.8
exceeded, the temperature increased very fast to higher
temperatures, which also affected the stability of the numerical a
The reactor dimensions are fixed: L = 3.43 m, D = 1 cm, d = 2 mm.

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the respective one-dimensional models. A larger discrepancy
exists between pseudohomogeneous and heterogeneous
models, where the latter ones predict lower conversions.
Also, the optimal temperatures of inlet gas and coolant as well
as the coolant parameter differ between pseudohomogeneous
and heterogeneous models. The inlet pressure is at the upper
bound for all models.
For a lower reactor load, the conversions are in general
higher due to a longer residence time, however, the space time
yield is lower. Since less reactants are converted, also less
reaction heat is released, and the required coolant flow is
smaller (higher Kc values). The other optimized inlet
conditions are milder, too. Differences in the predicted
conversions by the different models have the same trend as
in the high load case. For both load scenarios, the maximal
conversions are below the equilibrium conversion. In the
following, we present the results of each model in more detail
and discuss the discrepancies between the models.
One-Dimensional Pseudohomogeneous Model. The
conversion maximization according to the optimization
problem OP 1 is constrained by a maximal difference between
reactor and coolant temperature of 20 K. Therefore, the
resulting axial reactor temperature profile varies only in a range
of 10 K, and a severe hot spot is not formed (see Figure 1).
The temperature control in the tubular reactors is realized by
cooling in concurrent flow. The reaction heat causes an
increase of the coolant temperature with reactor length.
Figure 1. Reactor and coolant temperature profiles of the wall-cooled
fixed bed methanation reactor. Calculations are based on the 1D
pseudohomogeneous steady state reactor model and an inlet molar
flow of ntot,in = 3.85 × 10−2 mol/s.
In the 1D reactor model, the temperature and concentration
profiles are constant in the radial direction. This is a common
assumption for low heat and mass transfer resistances within
the fixed bed. The only two transport resistances which are
considered in the model are the heat transfer between the gas
and reactor wall and the effective radial heat transport of the
fixed bed. The aggregated thermal resistances are described by
the overall heat transfer coefficient kw (see eq 20). A low
resistance allows for a better heat removal by the coolant and
therefore is a key parameter for strong exothermic (or
endothermic) reactions.
Within the reactor, the heat transfer coefficient as the inverse
of the heat transfer resistance strongly decreases (see Figure
2). The overall heat transport coefficient is influenced by the
thermal conductivity of the gas phase and the superficial
velocity, which both decrease in axial direction considerably.
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Figure 2. Overall heat transfer coefficient calculated with the 1D
pseudohomogeneous steady state reactor model and an inlet molar
flow of ntot,in = 3.85 × 10−2 mol/s. The coefficient is closely linked to
the velocity field in the reactor. While the number of moles reduces
with reactor length, the velocity and heat transfer coefficient decrease
considerably. The velocity change is about 28%, and the change of the
heat transfer coefficient is about 40%.
The velocity reduction is mostly caused by the volume
reducing reaction and also slightly by the temperature and
pressure change. This affects the convective part of the heat
transport coefficient αw and the effective thermal conductivity
λeff
r of the bed. The thermal conductivity of the gas phase is
dominated by the high conductivity of hydrogen at the reactor
inlet but decreases with the conversion considerably. This
result demonstrates the importance of the axial velocity field
and nonconstant gas phase properties regarding the heat
removal in the reactor.
One-Dimensional Heterogeneous Model. In addition to
the overall heat transfer, the heterogeneous model considers
both the intrapellet heat and mass transfer resistance and the
resistance between the gas phase and pellet surface. Depending
on the pellet size and the magnitude of the transport
resistances, the temperature and concentrations within the
pellet differ from the gas phase. Therefore, the effective
reaction rate differs from the intrinsic rate. The ratio of
effective and intrinsic reaction rate is known as the catalyst
effectiveness. If a catalyst effectiveness factor is introduced to a
steady state pseudohomogeneous model, the model precision
can be improved. However, approximation methods of the
catalyst effectiveness without a heterogeneous model are often
insufficient due to the underlying assumptions.
The optimized reactor conditions calculated based on the
1D heterogeneous model show lower inlet gas and coolant
temperatures and a slightly smaller coolant flow in comparison
to the pseudohomogeneous model (see Table 2). The maximal
conversion is 81.98% and about three percentage points lower
than predicted by the pseudohomogeneous model. The
temperature and mole fraction profiles show large gradients
within the pellet (see Figure 3 and Figure 4). The exothermic
reaction and a rather low approximated thermal conductivity of
the pellet cause a temperature increase toward the pellet
center. However, only a small temperature difference forms
between the pellet surface and gas phase. High gas velocities
which are common for reactors with exothermic reactions are
beneficial for the gas−solid heat transfer. The simulation
reveals large concentration (or mole fraction) gradients within
the pellet, which are caused by the transport processes, i.e.,
pore diffusion. Similar to the heat transfer, the mass transfer
between the gas and pellet phase is very good.
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Figure 3. Temperature profiles of gas, pellet, and coolant phase
calculated with the 1D heterogeneous steady state reactor model and
an inlet molar flow of ntot,in = 3.85 × 10−2 mol/s. There are
considerable temperature differences between the gas and pellet phase
which increase in the direction of the pellet center. The maximal
temperature difference between the pellet center and gas phase is
14.0 K.
Figure 4. Mole fraction profiles of gas and pellet phase calculated with
the 1D heterogeneous steady state reactor model and an inlet molar
flow of ntot,in = 3.85 × 10−2 mol/s. There is no apparent influence by
film diffusion (dashed line: mole fraction at pellet surface) but a
considerable effect of the intrapellet mass transfer.
The simulation results reveal a considerable influence of
mass and heat transfer resistances which influence the catalyst
effectiveness. The effectiveness is defined as the mean
(effective) reaction rate within the pellet divided by the
reaction rate under gas phase conditions:
∫V r P dV
p
ηcat = G reasoned by the exponential temperature dependence of the
VPr (36)
The predicted effectiveness is greater than 1 for most of the
reactor, which is caused by higher temperatures within the
pellet than in the gas phase (see Figure 5). The reaction rate is
enhanced by the temperature hot spot within the pellet, which
is caused by the low thermal conductivity of the pellet.
Although the catalyst effectiveness is above 1, the optimal
conversion predicted by the model is lower in comparison to
the 1D pseudohomogeneous case. The reason is that the gas
phase temperature profile level, which is the basis for the
calculation of the effectiveness, is lower than for the
pseudohomogeneous case. Higher temperatures are not
possible without a violation of the coolant constraint or
other constraints.
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Figure 5. Catalyst effectiveness calculated with the 1D heterogeneous
steady state reactor model and an inlet molar flow of ntot,in = 3.85 ×
10−2 mol/s. Higher temperatures toward the pellet center increase the
reaction rate and lead to an effectiveness greater than 1.
Two-Dimensional Pseudohomogeneous Model. In con-
trast to the 1D models, within the 2D models the heat transfer
resistance at the wall and the effective radial conductivity are
not aggregated to one overall coefficient but are considered
separately. The optimal temperature profile of the 2D
pseudohomogeneous model shows radial temperature differ-
ences up to 15.8 K which are caused by the exothermic
reaction and the thermal resistance of the fixed bed (see Figure
6). Regarding the predicted optimal conversion, the prediction
Figure 6. Temperature profile calculated with the 2D pseudohomoge-
neous steady state model and an inlet molar flow of ntot,in = 3.85 ×
10−2 mol/s. Moderate temperature gradients develop in the radial
direction with a maximal temperature difference between the reactor
center and wall of 15.8 K.
is slightly higher than the respective 1D model. This is
reaction rate. An important finding is that the temperature
profile of the 1D model agrees well with the radial averaged
temperature profile of the 2D model (see Figure 7). This
demonstrates the good applicability of the 1D model for the
steady state modeling within this case study.
Two-Dimensional Heterogeneous Model. The most
complex steady state model discussed in this work is a 2D
heterogeneous model where all introduced heat- and mass
transfer resistances are considered. The optimal control
variables and the predicted conversion are very similar to the
values obtained from the 1D heterogeneous model (see Table
2). The radial temperature gradient of the gas phase is of
similar magnitude to that for the 2D pseudohomogeneous
model (see Figure 8). However, temperature differences
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Figure 7. Comparison of temperature profiles based on pseudoho-
mogeneous and heterogeneous steady state reactor models (gas
phase). For the 2D models (dashed lines), the radial averaged
temperature is displayed. The major discrepancy appears between
pseudohomogeneous and heterogeneous models, whereas the 1D and
2D models show similar results.
Figure 8. Temperature profile calculated with the 2D heterogeneous
steady state model and an inlet molar flow of n tot,in =
3.85 × 10−2 mol/s. Large temperature gradients form between the
gas phase and pellet center with a maximal difference of 26.6 K. The
maximal difference between reactor center temperature and temper-
ature at the wall is 16.4 K.
between the pellet center and gas phase increase toward the
reactor center as a result of higher reaction rates. The largest
difference is 26.6 K. The gas phase temperature profile
calculated by the 1D heterogeneous model matches well the
radial averaged temperature of the 2D model (see Figure 7).
Summary. The steady state carbon dioxide conversion of a
reactor with fixed dimensions is optimized using four different
models. The maximized conversions are in a similar range for
each model and deviate only within three percentage points.
The results show no clear benefit of using a 2D model since
the radial gradients are rather small. Heterogeneous models are
more conservative and predict a lower conversion than the
pseudohomogeneous models. In conclusion, the simple 1D
pseudohomogeneous model describes already quite well the
steady state temperature and concentration profiles in the
reactor and gives a good estimate of the achievable conversion.
However, based on the results, we strongly recommend to
consider the axial velocity profile and an axial variable overall
heat transport coefficient due to the volume reducing reaction.
4.2. Comparison of Dynamic Reactor Models. The
dynamic behavior of the methanation reactor is investigated
regarding a disturbance of the steady state operation point by a
positive or negative step change of the inlet molar flow rate.
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The predicted transition time until a new steady state or a
runaway is reached is measured according to the criteria in eq
34 and eq 35 and compared between the models (see section
3.2). At first, the reactor is at the steady state for a calculated
operation point (load) as described in the previous section.
Then, the flow rate is changed by an absolute value of Δṅin =
±3.85 × 10−3 mol/s, which is 10% of the high load case. Other
operation conditions, which are the pressure, gas, and coolant
inlet temperature and the coolant flow rate, are kept constant.
At first, the predicted reactor response on an increased flow
rate is compared for the different dynamic models. Then, a
negative step change is investigated. At last, the drawn
conclusions are tested within a parametric study.
Positive Step Change Simulation. Positive step changes of
the molar flow rate equal an increased volume flow and result
in an increased axial velocity profile and consequently shorter
residence times. The simulation of a step change from 100% to
110% of the inlet flow rate with the 1D pseudohomogeneous
model shows that the temperature level in the reactor
decreases and the hot spot moves toward the reactor outlet
(see Figure 9). The increased velocity improves the convective
Figure 9. Temperature variation in the reactor as a consequence of a
positive step change of the inlet molar flow from 100% to 110%
calculated with the 1D pseudohomogeneous model. A new steady
state is reached after 114 s.
axial heat transport and reduces the heat transfer resistance to
the reactor wall. The resulting lower reaction rates and the
shorter residence time cause a drop of the conversion (see
Figure 10). A new steady state is reached after 114 s.
A positive step change from a lower load operation point
(60% to 70% of the inlet flow rate) results in the same reactor
behavior with reduced temperature level and conversion.
However, the transition time until a steady state is reached
(162 s) is longer in comparison to the first case. At a lower
operation level, the gas velocity is also lower, which increases
the thermal resistance to the reactor wall, and thus longer
times are required until a new steady state is reached.
Positive step change simulations are also investigated for the
more complex, heterogeneous, and 2D models. The trend is
the same for all models: the temperature level decreases, and
the hot spot moves toward the reactor outlet while the
conversion decreases. Also, the transition time until a steady
state is reached increases for simulations from lower operation
points. However, the important discrepancy between the
models is the predicted time until the new steady state is
reached (see Figure 11). The 2D heterogeneous model
predicts a time until steady state, which is 91% longer than
predicted by the 1D pseudohomogeneous model for a step
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Figure 10. Temperature progress of the hot spot as a consequence of
a positive step change of the inlet molar flow from 100% to 110%
calculated with the 1D pseudohomogeneous model. With a lower
temperature and lower residence time, the conversion at the reactor
outlet decreases. A new steady state is reached after 114 s.
Figure 11. Results of a positive step change simulation of the total
inlet molar flow rate for different dynamic reactor models. A flow rate
of 100% refers to the molar flow rate of 3.85 × 10−2 mol/s. The
predicted times until a new steady state is reached differ considerably
between the models and increase with lower flow rates.
change from 100% to 110% of the inlet molar flow rate. In
general, the major differences appear between pseudohomoge-
neous and heterogeneous models regarding the predicted
transition time. Also, the 2D models both predict longer times
than the respective 1D models; however, the discrepancies are
only comparatively small. Apparently, the more transport
resistances are considered in the model, the longer is the
predicted time until a new steady state is reached.
The difference between the model prediction of the
pseudohomogeneous and heterogeneous reactor models can
better be understood by a closer examination of the dynamic
temperature change within a catalyst pellet. In Figure 12, the
temperature change within the pellet and the gas phase is
shown for a pellet at the axial position of 1.54 m. This position
equals the hot spot position for the initial steady state. Multiple
effects are visible. First, the data reveal that the temperature
change from one steady state to the new one differs within the
pellet and the gas phase. The temperature change at the pellet
center is 5.5 K. The change at the pellet surface is 5.1 K, and
the gas phase temperature change is 4.8 K. A second effect
appears within the first seconds of the step change simulations.
At the pellet center, the temperature first increases before it
drops to the new steady state temperature level. Due to the
positive step change, the conversion is immediately lower.
Therefore, the concentrations of the reactants are suddenly
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Figure 12. Pellet and gas phase temperatures for a dynamic
simulation based on the 1D heterogeneous reactor model at the
axial position of 1.54 m. Positive step change from 100% to 110% of
the inlet molar flow. A larger temperature variation is given in the
pellet center than in the gas phase. A new steady state is reached after
194 s. The circles indicate the nonequidistant discretization mesh.
The temperature values are displayed at the center of each control
volume.
higher in the reactor. When the mass transfer is faster than the
heat removal (larger thermal resistance), the new concen-
tration level of the gas phase reaches the pellet center at a still
high temperature, causing higher reaction rates and a
temperature increase. Basically, the same effect is responsible
for the wrong-way behavior of catalytic reactors. However, due
to the increased convective heat transport and a reduced heat
transfer resistance to the gas phase as a result of the positive
step change, the pellet temperature drops in the long term.
This example demonstrates that the pellet and gas phase
dynamic behavior differ as a result of mass and heat transfer
influences. It takes time until the heat of the pellet is dissipated
by the cooler gas phase and a new steady state of pellet and gas
phase is reached. In contrast to that, pseudohomogeneous
reactor models neglect these heat and mass transfer resistances.
Both the pellet phase and the gas phase have the same
temperature at all times, and therefore no time lag for the heat
dissipation is considered. As a result, the predicted times until
steady state are underestimated.
On the basis of the argumentation of transport resistances, it
seems reasonable that the 2D models predict similar times
until the steady state to those of the respective one-
dimensional models. Both model types consider the same
resistances but only in a different way.
Negative Step Change Simulation. The reduction of the
molar flow rate by a negative step change reduces the inlet
volumetric flow rate. This results in lower axial velocities and,
therefore, longer residence times. At first, the negative step
change from 100% to 90% of the inlet flow rate is discussed for
the 1D pseudohomogeneous reactor model. The results show
an increase of the hot spot temperature and a shift of the hot
spot toward the reactor inlet (see Figure 13). The model
predicts a new steady state with increased conversion after
206 s (see Figure 14). Apparently, the cooling is still sufficient
to maintain a stable reactor operation. The profile of the
coolant temperature changes only slightly as a consequence of
the shift of the hot spot. Due to a reduced total amount of
converted reactants, also the total amount of released heat in
the reactor is lower, and therefore, the outlet coolant
temperature decreases slightly. Although the conversion
increases, the space time yield decreases from 24.3 mol/m3s
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Figure 13. Reactor and coolant temperature progress of a dynamic
simulation based on the 1D pseudohomogeneous reactor model.
Negative step change from 100% to 90% of the inlet molar flow. A
new steady state is reached after 206 s.
Figure 14. Hot spot temperature progress and carbon dioxide
conversion of a dynamic simulation based on the 1D pseudohomoge-
neous reactor model. Negative step change from 100% to 90% of the
inlet molar flow rate. A new steady state is reached after 206 s.
to 23.1 mol/m3s due to the lower inlet molar flow rate.
However, it has to be noted that the new steady operation
point does not meet the coolant constraint of 20 K anymore.
Negative step change simulations are investigated using the
more complex reactor models as well. In contrast to the simple
1D pseudohomogeneous reactor model, the other models
predict a runaway of the reactor instead of a new steady state
operation point. On the basis of the results from the positive
change simulation, it could be assumed that the major
discrepancies appear between homogeneous and heteroge-
neous models. However, for the negative step change, the
results show a different trend. Both 2D models predict
considerably shorter times until runaway than the respective
1D models (see Figure 15).
For the reasoning of the listed observations, not only the
considered heat and mass transport resistances of the models
are important. A runaway of the reactor is a consequence of an
uncontrolled local increase of the reaction rate and heat
development due to insufficient cooling. Therefore, besides the
transport resistances the temperature dependency of the
reaction rate is an important factor.
The 1D heterogeneous model predicts a runaway after 190 s,
whereas the homogeneous model predicts a new steady state
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Figure 15. Results of a negative step change simulation of the total
inlet molar flow rate for different dynamic reactor models. A flow rate
of 100% refers to the molar flow rate of 3.85 × 10−2 mol/s. The
predicted times until the reactor runaway temperature threshold is
reached differ considerably between the models and decrease with
lower flow rates. The 1D pseudohomogeneous model does not
predict a runaway but a steady state for high reactor loads.
for a step change from 100% to 90% of the inlet molar flow
rate. Figure 16 shows the pellet and gas phase temperature at
Figure 16. Pellet and gas phase temperature of a dynamic experiment
at axial position 0.79 m. The temperature increase in the pellet center
is 35.5 K, while at the same time the gas phase temperature increases
only by 24.4 K. The circles indicate the nonequidistant discretization
mesh. The temperature values are displayed at the center of each
control volume.
the axial position of 0.79 m, which is at a position of a high
temperature increase. An interesting finding that reasons the
predicted runaway is that the pellet (center) temperature
increases considerably faster than the gas phase temperature.
The increasing pellet temperatures and insufficient heat
removal cause the acceleration of the reaction rate, and a
runaway is caused. Since the 1D pseudohomogeneous model
does not consider the thermal resistance within the pellet, the
model overestimates the heat removal, and a stable operation
of the reactor is more likely.
A very fast runaway of the reactor is predicted by both 2D
models. As shown in the results of the steady state reactor
models, 2D models describe higher temperatures in the reactor
center than at the reactor wall due to the thermal resistance of
the fixed bed (see Figure 6 and Figure 8). As expected, for the
dynamic simulations, the temperature threshold characterizing
a runaway (eq 35) is exceeded first at the reactor center as
shown in Figure 17. In the figure, the temperature progress of
the radial averaged temperature is displayed also. The
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Figure 17. Comparison of the tube center and radial averaged
temperature progress of a dynamic simulation based on the 2D
pseudohomogeneous reactor model. Negative step change from 100%
to 90% of the inlet molar flow rate. The runaway threshold is
exceeded after 94 s.
temperature profile is useful for a comparison with a 1D
model, where the temperature profile is a radial averaged value
as well. The temperature increase in the reactor center is
considerably faster in comparison to the mean temperature
because of the temperature dependency of the reaction rate
and the thermal resistance of the fixed bed.
The shortest time until runaway is predicted by the 2D
heterogeneous model. In comparison to the other models, not
only is the time shorter but also the axial position of the
runaway differs. Figure 18a shows that the temperature near
the reactor inlet increases faster than at the initial hot spot
position. The increasing gradients between pellet center and
gas phase in the radial reactor direction were already discussed
for the steady state case. For the dynamic case, the runaway at
the reactor inlet is caused by a fast increase of the pellet
temperature at the reactor inlet as shown in Figure 18b.
A negative step change of the molar flow rate is also
investigated for a lower operation point to investigate the
influence of the gas velocity on the dynamic behavior. For a
step change from 60% to 50% of the inlet molar flow rate, each
reactor model predicts a runaway of the reactor (see Figure
15) including the 1D pseudohomogeneous model. Further-
more, the predicted times until runaway are considerably
shorter than for a higher operation point. Obviously, the
reduced velocity and heat transfer accelerate the runaway.
Figure 18. Gas phase (a) and pellet center (b) temperature progress at the tube center of a dynamic simulation based on the 2D heterogeneous
reactor model. Negative step change from 100% to 90% of the inlet molar flow rate. The runaway threshold is exceeded after about 78 s.
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Again, the 2D models predict a faster runaway than the
respective 1D models.
Summary. The results of dynamic step change simulations
reveal large discrepancies between the different model
predictions. The models predict considerably different times
until a new steady state is reached or a runaway behavior
develops. None of the simpler models is able to well represent
the prediction of the complex 2D heterogeneous model for all
cases. The trends indicate that the transport resistances in the
model strongly influence the dynamic reactor behavior and,
therefore, provide the reason for the discrepancies between the
models. In conclusion, while the predictions of the steady state
models are very similar, this is not the case for the dynamic
models.
4.3. Parametric Study. The results of the model
comparison indicate that the consideration of heat and mass
transfer resistances considerably impacts the prediction of the
dynamic reactor behavior. Especially, the intrapellet resistan-
ces, which are only considered by heterogeneous models with
nonisothermal pellet balances, are important. However, in the
literature, it is also discussed that pseudohomogeneous models
are rather not suitable to describe the dynamic reactor
behavior in general. The reason is assumed to be in the
different storage capacities of the catalyst and gas phase.38
Therefore, we try to further substantiate our findings by a
parametric study of the intrapellet mass and heat transfer
resistances in this section. The magnitude of the intrapellet
transport resistances is varied and the effect on the dynamic
model prediction is examined.
On the basis of the dynamic 1D heterogeneous reactor
model, the thermal conductivity of the catalyst λcat and the
component diffusion components Dα,y within the pellet
balances (eq 3 and eq 4) are manipulated by a factor in
order to increase or decrease the value. A factor greater than 1
decreases the transport resistance, whereas lower factors
increase the respective resistance. The other transport
resistance, e.g., the resistances between the gas phase and
catalyst surface as well as the effective conductivity of the fixed
bed, remain unchanged. Regarding the catalyst conductivity,
four factors are considered (1, 2, 4, and 6). A factor of 6 results
in a pellet conductivity of 0.9 kW/Km. The diffusion
coefficients are manipulated by four factors (0.5, 1, 2, and 4)
also. A manipulation of the diffusion coefficient can also be
interpreted as a change of the assumed catalyst properties such
as porosity and tortuosity.
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On the basis of the manipulated model, the dynamic reactor
behavior is investigated according to the outlined method-
ology. A positive step change from 100% to 110% of the inlet
molar flow rate is investigated. All combinations of factors are
considered, which results in 16 cases. As a reference, the results
are compared to the 1D pseudohomogeneous model, where
the intrapellet resistances are neglected (infinitely low).
The parameter variation shows that with increasing thermal
conductivity of the pellet, the time until the steady state is
reached decreases and approaches the predicted time of the 1D
pseudohomogeneous model (see Figure 19). A higher thermal
Figure 19. Parametric study of intrapellet transport resistances and
their effect on the dynamic model prediction. Time until steady state
for a positive step change from 100% to 110% of the inlet molar flow
rate based on a manipulated 1D heterogeneous model. The dashed
line represents the 1D pseudohomogeneous reference case with a
time until steady state of 114 s.
conductivity causes a faster heat removal within the pellet
during the step change. With lower transport resistances, the
temperature and concentration gradients within the pellet
disappear. The remaining differences in the predicted time are
caused by the transport resistance between the gas phase and
pellet surface. A further test simulation with very low
intrapellet resistances and also low resistances between the
gas and pellet surface showed that the simulation matches the
results of the pseudohomogeneous model perfectly.
An interesting result is that for a constant thermal
conductivity, the time until the steady state increases with
higher diffusion coefficients. A faster diffusion rate causes
higher concentrations of reactants within the pellet and higher
reaction rates. In this case, more heat is released, which
counteracts the temperature decrease of the pellet, and thus
the time until steady state is longer. A slow diffusion has just
the opposite effect.
The parametric study supports our finding that both heat
and mass transfer resistances have a great impact on the
dynamic reactor behavior. The different storage capacities of
the phases are important, but they are considered in the
accumulation terms of both the heterogeneous and pseudo-
homogeneous model consistently. If the intrapellet transport
resistances and the resistances between the phases are very
low, the dynamic behavior can also be described by a
pseudohomogeneous model quite reasonably despite the
different storage capacities.
5. CONCLUSIONS
The detailed comparison of steady state and dynamic reactor
models for the methanation of carbon dioxide in a wall-cooled
fixed bed reactor reveals the importance of heat and mass
19418
Article
transfer, which is particularly relevant for the dynamic model
prediction. The investigated model complexity reaches from a
simple 1D pseudohomogeneous formulation to a 2D
heterogeneous model.
A maximization of the carbon dioxide conversion using each
steady state reactor model shows that similar conversions are
predicted based on the same optimization constraints and fixed
reactor dimensions. Discrepancies occur especially between
pseudohomogeneous and heterogeneous models where the
latter consider the catalyst effectiveness correctly and are, thus,
more conservative. The simple 1D pseudohomogeneous model
describes the temperature and concentration progress well in
the reactor and gives a close estimate of the maximal
conversion.
The major focus of this work is dynamic simulations of step
changes of the molar inlet flow rate. An increased flow rate
results in a new steady state operation point with reduced
conversion due to shorter residence times and lower
temperatures. The important finding is that large discrepancies
occur between the models regarding the predicted transition
time until a new steady state is reached. A parametric study
reveals that the difference is caused by the magnitude of
intrapellet mass and heat transport resistances. Pseudohomoge-
neous models completely neglect the heat and mass transfer
resistances within the catalyst and between the phases, which
results in significantly faster times until a steady state is
reached. The negative step change of the molar flow rate
quickly leads to a runaway of the reactor due to lower
convective heat removal and a higher heat transfer resistance at
the reactor wall. Again, considerably different times until
runaway are predicted by the models. Remarkably, for this
case, 2D models predict a considerably faster runaway than the
respective 1D models due to higher temperatures and reaction
rates at the tube center.
Our study shows the importance of heterogeneous and two-
dimensional models for the description of the dynamic reactor
behavior. If the transport resistances are non-negligible, the
dynamic model prediction varies strongly between both
heterogeneous and pseudohomogeneous models. Furthermore,
2D models are important for the dynamic simulation of
scenarios where the reactor is stressed by a decreased heat
removal. In this case, a 2D model predicts a runaway
considerably faster than a 1D model. Nevertheless, for low
intrapellet transport resistances a simplified model such as a
heterogeneous model with isothermal pellet balances or a
pseudohomogeneous model is also capable of describing the
dynamic reactor behavior sufficiently.
■
ASSOCIATED CONTENT
* Supporting Information
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.iecr.9b02863.
Overview of all model derivatives; model based reactor
design; remarks on model comparison methodology
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +49 (0)9131 85-70419. E-mail: hannsjoerg.freund@
fau.de
ORCID
Konrad L. Fischer: 0000-0003-2029-1485
DOI: 10.1021/acs.iecr.9b02863
Ind. Eng. Chem. Res. 2019, 58, 19406−19420
Industrial & Engineering Chemistry Research Article

Notes p (bar) = Partial pressure

The authors declare no competing financial interest. Pe = Peclet number

■ ACKNOWLEDGMENTS
The authors gratefully acknowledge the funding of the
Pr = Prandtl number
r (m) = Radial reactor coordinate
ri (kmol/s) = Rate of reaction i
Bavarian State Government within the framework of the Re = Reynolds number
Energie Campus Nürnberg (EnCN). Furthermore, the authors T (K) = Temperature
gratefully thank the German Research Foundation (DFG) for Sv (m2/m3) = Specific surface area of catalyst pellet
financial support within the Priority Program SPP 2080 Sc = Schmidt number
“Catalysts and Reactors under Dynamic Conditions for Energy Sh = Sherwood number
Storage and Conversion.” t (s) = Time

■
tf (s) = End time
NOMENCLATURE vc (m/s) = Coolant velocity
vz (m/s) = Superficial gas velocity
Abbreviations wα = Mass fraction of component α
1D Hom. = One-dimensional, pseudohomogeneous reactor xα = Mole fraction of component α
model X = Conversion
2D Hom. = Two-dimensional, pseudohomogeneous reactor y (m) = Radial pellet coordinate
model z (m) = Axial reactor coordinate

■
1D Het. = One-dimensional, heterogeneous reactor model
2D Het. = Two-dimensional, heterogeneous reactor model
SNG = Synthetic natural gas INDEX

■ GREEK LETTERS
α = Component (CO2, H2, CH4, H2O)
0 = Initial conditions
cat = Catalyst pellet
c = Coolant
αGP (kW/m2/K) = Gas particle heat transfer coefficinet in = Reactor inlet
αw (kW/m2/K) = Heat transfer coefficient at the wall P = Pellet phase
βGP (m/s) = Gas particle mass transfer coefficient s = Solid
δ (m2/s) = Diffusion coefficient tot = total

■
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