chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

journal homepage: www.elsevier.com/locate/cherd

A fixed-bed reactor modeling study on the

methanation of CO2

David Schlereth, Olaf Hinrichsen ∗

Catalysis Research Center and Chemistry Department, Technische Universität München, D-85748 Garching b.
München, Germany

a b s t r a c t

The methanation of carbon dioxide has gained renewed interest during the last years as a possible technology to
synthesize a feasible chemical energy carrier. This modeling study aims at a basic understanding of the aspects
relevant for designing an externally cooled fixed-bed reactor for the methanation of a pure, stoichiometric feed
gas. It is shown that the reaction rates and the exothermicity (H◦ = −165 kJ/mol) prevent a fixed-bed reactor of
technical dimensions to be operated at high conversions without runaway of the reactor. The model predictions of
differently detailed pseudo-homogeneous reactor models and a heterogeneous reactor model where the intraparticle
transport of mass is described according to a dusty-gas approach are compared to assess the needed level of detail
in terms of modeling the heat transfer, fluid flow characteristics and transport resistances on the pellet scale. Under
specific conditions, intraparticle mass transfer and external heat transfer need to be considered for describing the
temperature and concentration profiles adequately. The study is completed by modeling a fixed-bed membrane
reactor as an example of a structured reactor that offers improved temperature control by separated and controlled
feeding of hydrogen and carbon dioxide.
© 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Methanation; Sabatier reaction; Carbon dioxide; Reactor modeling; Reactor design; Dusty-gas model

1. Introduction been established and essential questions concerning catalytic

systems, kinetics and reaction engineering have not been
The transition of the energy supply from conventional toward answered yet. The renewed interest in the Sabatier reaction
renewable resources implies the need for adequate energy during the last years has provoked efforts primarily in devel-
storage technology and capacity as a consequence of the oping new and improved catalytic systems and studying the
unsteady onset of wind and solar energy. The electrolysis of mechanism on different catalytic systems both experimen-
water and the reaction of hydrogen with carbon dioxide to tally by spectroscopy and theoretically by DFT calculations.
methane offer a possible next generation storage technology For example, Park and McFarland (2009) investigated a
(Sterner, 2009): Pd-Mg/SiO2 catalyst in detail and compared it to other mul-
ticomponent systems where Mg was replaced by various
CO2 + 4H2  CH4 + 2H2 O H◦ = −165 kJ/mol metals. A bifunctional mechanism was proposed where car-
Biomass, flue gases from power plants or emissions of bon dioxide is first adsorbed on a magnesium containing oxide
the cement industry at lime burning are thought of as pos- species while highly dispersed Pd(0)-particles provide atomic
sible sources for carbon dioxide. Being a feasible chemical hydrogen via spillover for reducing carbon dioxide selec-
energy carrier, methane can easily be stored, transported and tively to methane. They confirmed this mechanism by DFT
converted back into electric energy while solely employing calculations and a carbon dioxide temperature-programmed
existing infrastructure and technology. Though the metha- desorption study later on (Kim et al., 2010). Extensive work
nation of carbon dioxide has been well known since the was carried out by Vesselli et al. (2008, 2010, 2011) in
beginning of the 20th century, no commercial process has studying the mechanism on metallic Ni experimentally and

∗
Corresponding author. Tel.: +49 8928913232; fax: +49 8928913513.
E-mail addresses: [email protected] (D. Schlereth), [email protected] (O. Hinrichsen).
Received 2 August 2013; Received in revised form 8 November 2013; Accepted 13 November 2013
0263-8762/$ – see front matter © 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cherd.2013.11.014
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712 703

due to the high reaction rates transport limitations might

Nomenclature affect the catalyst performance under technical conditions.
In order to assure a precise temperature control, Brooks et al.
Di Knudsen diffusion coefficient of component i (2007) developed a microchannel reactor for the Sabatier
(m2 /s) process intended for producing 16 g/h of methane for usage
Dij binary diffusion coefficient of component i in j in space-related applications, i.e. propellant production on
(m2 /s) Mars. A Ru-based catalyst system was chosen, for which a
Dr eff radial dispersion coefficient (m2 /s) kinetic rate equation was fitted to experimental data. The
H◦ standard reaction enthalpy (J/mol) performance of the microchannel reactor could successfully
Nu Nusselt number, kh dp /g be simulated by solving mass, momentum and energy bal-
Pr Prandtl number, cp,m /g ances. Sudiro et al. (2010) simulated a structured catalytic
Re Reynolds number, udp / reactor consisting of an externally cooled reactor tube loaded
Sc Schmidt number, /Dij with metallic honeycomb catalysts for the methanation of
Sh Sherwood number, km dp /Dij a mixture of CO and CO2 using a 1D heterogeneous single-
T temperature (K) tube model. At the Paul Scherrer Institut, the fluidized-bed
Tc cooling temperature (K) technology has been studied in detail for the methanation
UA heat transfer coefficient (W/(m2 K)) of biomass-derived feed gases (Kopyscinski, 2010; Seemann
X conversion et al., 2006). Generally, the methanation of synthesis gas
Y yield from coal or biomass which is characterized by high carbon
c concentration (mol/m3 ) monoxide content has by now attracted more attention both
cp molar heat capacity J/(mol K) by industry and academia, see for example the review by
cp,m specific heat capacity J/(kg K) Kopyscinski et al. (2010) on SNG processes.
dp pellet diameter (m) This reactor modeling study aims at gaining insight in reac-
dpore pore diameter (m) tion engineering aspects relevant for fixed-bed reactors in the
dtube tube diameter (m) methanation of a pure, stoichiometric gas mixture of CO2 and
f1 , f2 coefficients from Ergun’s equation H2 . Though also networks of adiabatic reactors with bypassing
p pressure (Pa) and recycle streams well known from SNG processes could be
r radius/radial coordinate (m) adopted to the CO2 methanation the focus is laid on externally
rj reaction rate of reaction j (mol/(kgcat s)) cooled, single-pass fixed-bed reactors of dimensions typically
u axial velocity (m/s) found in tube-bundle reactors, since in the power-to-gas con-
xi mole fraction of component i cept the reactor needs to be started and shut down fast and
y radial coordinate (m) easily as well as be capable of handling load changes.
z axial coordinate (m) At first, different pseudo-homogeneous reactor models will
 radial dispersion coefficient (W/(m K)) be compared in order to evaluate the level of detail needed
˝ molar flux density (mol/(m2 s) in modeling of the heat transfer and fluid flow characteris-
˛ wall heat transfer coefficient (W/(m2 K)) tics. Secondly, results for a heterogeneous reactor model and
ˇ Prater number the influence of transport phenomena on the reactor perfor-
ε pellet porosity mance will be discussed. Based on these results, the potential
j effectiveness factor for reaction j of structured reactors will be highlighted by simulating a fixed-
 thermal conductivity (W/(mK)) bed membrane reactor.
 dynamic viscosity (Pa s)

i,j stoichiometric coefficient of component i in
reaction j 2. Model development
 density (kg/m3 )
 tortuosity 2.1. Kinetics
bed porosity
The focus is laid on Ni-systems since from an economic
point of view any different choice must offer considerable
theoretically. Via UHV techniques certain surface interme- improvements in activity and selectivity. Nevertheless, this
diates of a mechanism proposed for a (1 1 0) surface by study will also help to clarify the requirements for other cat-
DFT calculations were detected spectroscopically. Besides, in alytic systems because – as will be shown – heat management
transient kinetic experiments under ambient pressure the on the reactor scale and transport phenomena are of par-
methane formation on highly dispersed Ni(0) was studied in ticular importance. Concerning Ni-systems, Weatherbee and
detail. It was found that the adsorption of carbon dioxide is Bartholomew (1982) published Langmuir–Hinshelwood rate
strongly affected by the presence of hydrogen. The results of equations for Ni/SiO2 describing the intrinsic kinetics at a total
the transient kinetic runs could be explained by two reactions pressure of 1.4 bar, temperatures between 500 and 600 K and
operating in parallel (Vesselli et al., 2011). Except for Ni and space velocities between 30,000 and 90,000 h−1 . Since the mole
Pd, also Ru and Rh have been shown to be catalytically active fractions of hydrogen (carbon dioxide) were varied between
for the CO2 methanation (see e.g. Brooks et al., 2007; Kusama 2% and 10% (0.2% and 2.0%), the partial pressures are con-
et al., 2000). siderably lower than in a technical process operating at the
Less attention has been paid to reaction engineering stoichiometric feed gas composition at elevated pressure. For
aspects for the Sabatier process so far though the high this study, the rate equations proposed by Xu and Froment
exothermicity calls for consideration of the heat manage- (1989) for the intrinsic kinetics of the steam reforming, CO2
ment and the coupling of heat and mass transfer. Moreover, methanation and the reverse water–gas shift reactions on
704 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712

∂T  3

heat balance : (uctot )c̄p = bed rj (−R Hj )

∂z
j=1

4
− U (T − Tc ) (2)
dtube A

The pressure drop along the axial reactor coordinate is

neglected and the partial pressures pi of the components
are calculated assuming ideal gas behavior. The specific heat
capacity cp,i of component i is calculated with the Shomate
equation using data from the NIST database. It was fur-
thermore verified that for the chosen conditions the cooling
temperature can well be approximated as constant in case of
a molten salt reactor for example. UA  describes an effective,

overall heat transfer coefficient that results from a series of

− resistances caused by the effective heat transfer coefficient
for the tube insight, the conductivity of the metallic tube wall
and the heat transfer coefficient for the tube outside. The
−
resistance of the tube wall is neglected and the heat transfer
coefficient for the tube outside is set constant to 2000 W/(m2 K).
−
1 1 1
UA = ˛ +
˛out
(3)
eff

According to de Wasch and Froment (1972), in a 1D model

Scheme 1 – The kinetic model by Xu and Froment.
the effective heat transfer coefficient for the tube insight can
Ni/MgAl2 O4 are used (see Scheme 1). The conditions for the be approximated by
methanation and reverse water–gas shift experiments were
temperatures between 300 and 400 ◦ C and pressures between 1 1 d
= + tube (4)
3 and 10 bar at undiluted feed gas compositions. An excel- ˛eff ˛W 8eff
r
lent fit of the data was obtained by Xu and Froment with
Langmuir–Hinshelwood–Hougen–Watson rate equations (Xu assuming again a series of resistances concerning the wall
and Froment, 1989). heat transfer coefficient and the radial dispersion of heat. ˛W
Aparicio (1997) used the data by Xu and Froment and sup- characterizes the heat transfer adjacent to the wall while effr
plemented them by transient experiments, i.e. concerning describes the transport in the fixed-bed. According to the VDI-
transient CO methanation runs, to develop a comprehensive Wärmeatlas the radial dispersion and the effective wall heat
elementary step kinetic model. In order to justify the usage transfer coefficient are split into a stagnant and a dynamic
of the methanation kinetics developed for a typical steam contribution each (Tsotsas, 2006a,b), see Eqs. (A.1)–(A.5) in the
reforming catalyst, we also compared the kinetics to data appendix for details about the correlation equations. The ther-
recently published for the methanation of a stoichiometric mal conductivity of the gas mixture is calculated by the mixing
feed gas composition on Ni/ZrO2 by Schoder et al. (2013). After rule of Wassiljeva, where the temperature dependent thermal
merely adjusting the number of active sites (to 46% of the fresh conductivity and viscosity are approximated by polynomials
Ni/MgAl2 O4 catalyst by Xu and Froment) the kinetics describes using data from the VDI-Wärmeatlas (Kleiber and Joh, 2006).
the temperature and pressure dependence at the stoichiomet-
ric feed gas composition adequately though the model slightly 2.2.2. Two-dimensional, pseudo-homogeneous reactor
overestimates the apparent activation energy (see Fig. S1 in models
the supplementary information). In view of the different metal In order to take the radial profiles of temperature and gas
loading (15.2% and 5%) and oxide carrier of the catalyst sys- composition into account, also two-dimensional models were
tems, the ratio concerning the number of active sites seems implemented. The ˛W model assumes constant values of the
in a plausible range. In total, the excellent fit of the steady- properties describing the pseudo-homogeneous continuum,
state data by Xu and Froment, the previous usage of the data i.e. porosity and dispersion coefficients are independent of the
for developing a comprehensive microkinetic model and the radial position. Heat and mass transfer balances are formu-
adequate description of steady state data on Ni/ZrO2 validate lated as follows:
this kinetics for a reactor modeling study.
 3  
∂(uci ) ∂2 ci 1 ∂ci
2.2. Modeling of fixed-bed reactors mass balance : = bed
i,j rj + Deff
r +
∂z ∂r2 r ∂r
j=1
(5a)
2.2.1. One-dimensional pseudo-homogeneous PFR model
The simplest model used is a one-dimensional pseudo-
homogeneous plug-flow reactor (PFR) model. Mass and heat ∂T  3
heat balance : (uctot )c̄p = bed rj (−R Hj )
balances are formulated as follows: ∂z
j=1

 3  
∂(uci ) ∂2 T 1 ∂T
mass balance : = bed
i,j rj (1) + eff
r + (5b)
∂z ∂r2 r ∂r
j=1
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712 705

1.0 3.0 In addition to the mass and energy balances also the extended
Brinkman equation is solved as momentum balance. After the
0.8 implementation of an effective viscosity (Giese, 1997), that
accounts for turbulent flow fluctuations in the packed bed,
2.0

u(r)/u0 [-]
0.6 the superficial velocity field can be modeled.
ψ [-]

 
0.4 ∂p  ∂ ∂u(r)
1.0 = −f1 u(r) − f2 u2 (r) + eff r (8)
∂z r ∂r ∂r
0.2
with f1 , f2 from Ergun equation
0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 eff
r/rtube [-] and = 2 exp(2 × 10−3 Re)
gas

Fig. 1 – Radial profiles of the normalized axial velocity in

The example of a radial flow profile for the axial superfi-
the (r)-model and of porosity according to Giese’s
cial velocity u(r) in Fig. 1 illustrates a bypassing flow close to
correlation.
the wall which is in accordance with the high porosity in this
In the ˛W model a third type boundary condition is region. The velocity at r = rtube is 0 as a consequence of the
introduced to consider the resistance for the heat transfer non-slip boundary condition.
close to the wall. The wall heat transfer coefficient ˛W and
effective heat dispersion coefficient eff r are identical to the 2.2.3. Particle model for the one-dimensional,
contributions of the effective heat transfer coefficient in Eq. (4) heterogeneous PFR model
for the 1D model in Section 2.2.1. The mass dispersion coeffi- In order to quantify the effects of transport phenomena on
cient is calculated analogously to Eq. (A.1) where the molecular the reactor performance, the 1D pseudo-homogeneous reac-
Péclet number is used and the diffusion coefficient is sub- tor model is extended to a heterogeneous reactor model, i.e.
stituted for the thermal conductivity (see Tsotsas (2006b) for coupled balances for the reactor and the pellet level are solved
details). The boundary conditions for the ˛W model are: now. On the reactor level, the reaction rates in the mass and
∂T ∂ci the energy conservation are substituted for effective reaction
r=0: = 0, =0
∂r ∂r rates.
dtube ∂T  ∂ci
r= : eff
r = UA (T − Tc ), =0
2 ∂r ∂r rjeff = j rjintrinsic (9)
with
1 1 1
 = + As a particle model the dusty-gas approach is chosen
UA ˛w ˛out
for calculating the effective reaction rates because a net-
In contrast, the so-called (r)-model is based on a radial work of three reactions in a five-component system has to
distribution of porosity (Winterberg et al., 2000). Numerous be considered. It accounts for the transport mechanisms
empirical equations have been published to describe the of molecular and Knudsen diffusion as well as for viscous
porosity profiles as a function of shape and dimension of pel- flow. By this model no further assumptions and parameters
let and tube. Here, an empirical equation by Giese (1997) for except the pore radius, the tortuosity for the effective diffu-
spherical catalyst pellets in circular tubes is used. It considers sion coefficients as well as the permeability B0 for viscous
a porosity close to 1 near the tube wall that decreases mono- flow are introduced. The latter one is approximated by the
tonically toward the center to the value of 0.4 for infinite beds Hagen–Poiseuille law for laminar flow in a capillary. Pore radii
(see Fig. 1): rpore can easily be obtained experimentally via BET or Hg-
porosimetry. For setting up the dusty-gas model (DGM) the
  
rtube − r formalism developed by Skrzypek et al. (1984) is adopted. In a
(r) = 0.4 1 + 1.36 exp −5 (6)
dp system of N components and M reactions, M differential equa-
tions are solved for the molar flux densities ˝j correlated to
In the (r)-model, the overall heat transfer coefficient is the reaction j, (N − 1) differential equations for mole fractions
equivalent to the wall heat transfer coefficient at the tube xi of the components 1 − (N − 1) and one differential equation
outside: for the total pressure p.

1 1
 = (7) d˝j
UA ˛out = y2 rj j = 1, 2, 3 (10a)
dy
Consequently, it characterizes the heat transfer from the
⎛ ⎞
cooling medium to the tube inner wall (the resistance due to
dxi 1 
3

5
conduction in the metallic wall is neglected). The introduction =− 2 ⎝ ˝j
k,j Fik ⎠ i = 1, 2, 3, 4 (10b)
dy y
of an artificial wall heat transfer coefficient for the tube inside j=1 k=1
can be avoided in this model as the heat dispersion coefficient
is a function of the radial position and thus also captures the ⎛ ⎞
resistance adjacent to the tube wall (see Eq. (A.6)). This way, dp 1 RT 
5
1 
3
=− 2 ⎝
j,i ˝j ⎠ (10c)
there is no artificial jump in temperature between the inner dy y w Deff
i=1 i j=1
tube wall and the continuum phase but a continuous profile.
706 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712

CO2 H2
Table 1 – Boundary conditions for dusty-gas model.
˝j = 0 j = 1, 2, 3
y=0 dT
dy
=0


3
p

i,j ˝j = km RT (xi − xireactor ) i = 1, 2, 3, 4
y = rp
j=1 catalyst
p = preactor

3

˝j (−R Hj ) = kh (T − T reactor )
j=1

membrane
with
 
Scheme 2 – The principle of a fixed-bed membrane reactor.
RT 1 
5
xk xi B0 p 1
Fii = + − 1+
p Deff Deff Deff Deff w 2.3. Computational methods
i k=1 ik i i

The systems of ordinary and partial differential equations

   
RT xi xi B0 p 1 in the 1D pseudo-homogeneous PFR model, the ˛W , the het-
Fik = − + 1+
p Deff Deff Deff w erogeneous and the fixed-bed membrane reactor model were
ik k i
solved numerically in Matlab® . For ODEs the solver ode15s was
used. In the 2D-model the PDEs were transformed to ODEs via
B0 p  xi
5
orthogonal collocation. The boundary value problem on the
w=1+
Deff particle level of the heterogeneous model was solved with the
i=1 i
bvp4c-solver. For the (r)-model Comsol Multiphysics® was
employed.
2
rpore
B0 =
8 3. Results and discussion
The heat balance for the particle level is formulated as follows:
3.1. Thermodynamics

2 dT d2 T  3

P + P 2 + cat rj (−R Hj ) = 0 (11) Before discussing and comparing the results of the different
y dy dy reactor models, thermodynamic aspects of the CO2 methana-
j=1
tion are elucidated briefly. Fig. 2 shows the yield of methane in
thermodynamic equilibrium for the pure, stoichiometric feed
The effective diffusion coefficients Deff
i
and Deff
ij
are corre-
gas composition of H2 /CO2 = 80/20 considering the species
lated by the factor ε/ to the molecular and Knudsen diffusion
CO2 , H2 , CH4 , H2 O and CO. Since the methanation is a highly
coefficient which are approximated by Fuller’s equation and by
exothermic reaction with volume contraction, the highest
the kinetic theory of gases according to Eq. (12), respectively.
yields are obtained at low temperatures and high pressures.
 For e.g. a yield above 98% at a total pressure of 10 bar, the tem-
2 8RT perature needs to be below 300 ◦ C. If the pressure is reduced
Di = rp (12)
3 Mi to 1 bar, this temperature is shifted to 235 ◦ C. In contrast
to the yield the conversion rises again at temperatures of
The boundary conditions are summarized in Table 1. Heat above 600–800 ◦ C depending on the pressure. The selectiv-
and mass transfer coefficients for the particle-to-fluid transfer ity is shifted now toward carbon monoxide because of the
are approximated by Wakao’s correlation (Wakao et al., 1979): endothermicity of the reverse water–gas shift reaction. In ther-
modynamic equilibrium, the CO content at 1 bar is in the low
Sh = 2 + 1.1Sc1/3 Re0.6 (13a)
1.0
Nu = 2 + 1.1Pr1/3 Re0.6 (13b)
0.8
2.2.4. One-dimensional pseudo-homogeneous reactor
Ymethane [-]

model for a fixed-bed membrane reactor 0.6

In the fixed-bed membrane reactor a component is fed via a
membrane to the reactor (Scheme 2). The flux density ˝mem 0.4
through the membrane causes an additional source term in
the mass and energy balance (see Eqs. (A.7) and (A.8) in the 0.2
appendix). It is assumed that the pressure drop of the mem-
brane is large compared to the pressure drop in the fixed-bed 0.0
and the central tube so that the flux density ˝mem is con- 200 400 600 800 1000
stant over the whole reactor length. The heat transfer from
the annulus to the central tube was also taken into account. Fig. 2 – Yield of methane in thermodynamic equilibrium for
The hydraulic diameter was employed as characteristic length the stoichiometric feed gas composition (CO2 = 20%,
for correlation equations. H2 = 80%).
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712 707

800
Table 2 – Parameters in the reference case.
Space velocity GHSV 5000 h−1
Catalyst mass mcat 3 kg
Flow rate Q 10.9 Nm3 h 600
Total pressure p 10 bar
Feed mole fraction H2 x0 (H2 ) 0.8
Feed mole fraction CO2 x0 (CO2 ) 0.2
400
Pellet diameter dp 3 mm
Catalyst density cat 2350 kg m3
Bed density bed (1 − )cat
Bed porosity 0.4
200
Cooling temperature Tc Tfeed 200 300 400
Pore diameter dpore 20 nm
Tortuosity  4
1.0

ppm-range (<50 ppm) for temperatures below 300 ◦ C. Thus, 0.8

thermodynamically it is possible to produce a synthetic natu-
ral gas that can be fed into the natural gas grid without further 0.6
purification and separation steps except for the removal of
water from the product gas. 0.4

3.2. Parametric sensitivity and runaway behavior 0.2

At first, the parametric sensitivity concerning the feed and 0.0

200 300 400
cooling temperature is investigated using the 1D pseudo-
homogeneous reactor model for the stoichiometric feed gas
composition of H2 /CO2 = 80/20 at a tube diameter of 2 cm and Fig. 4 – Maximum temperature and yield as a function of
a total pressure of 10 bar. The reference conditions are sum- feed temperature in dependence on the tube diameter.
marized in Table 2. If not specified otherwise, results relate
to these data. Fig. 3a shows that for a feed temperature of
279 ◦ C a moderate hot spot with a temperature rise of about Fig. 4 for instance illustrates the influence of the tube diameter
11 ◦ C is developed and a yield of 32% methane is obtained. A on the reactor performance. Lowering the tube diameter, the
temperature rise of 3 ◦ C provokes a pronounced hot spot and radial heat dispersion is facilitated because of shorter trans-
significantly raises the yield to 40.8%. A further increase in port distances and higher Reynolds numbers. Consequently,
the feed temperature causes the runaway of the reactor: the the reactor is operated isothermally up to higher tempera-
heat release due to the chemical reaction exceeds the heat tures. Nevertheless, operation points with moderate hot spots
removal potential. The maximum temperature is above 690 ◦ C are not found. The formation of a hot spot provokes a runaway
now and a yield of 91.9% is obtained. According to the phase even at a tube diameter of 1 cm. However, the heat removal is
diagrams in Fig. 3b the methanation reaction runs into equi- so efficient that the region of parametric sensitivity is shifted
librium in the hot spot (Y ≈ 50%) for the feed temperature of to temperatures >305 ◦ C and yields <70% are obtained. In addi-
285 ◦ C. While cooling down, the equilibrium is shifted and the tion to severe fluid flow maldistribution effects at the low
methanation proceeds. Nevertheless, falling below a certain dtube /dp -ratio, that are not taken into consideration in the
temperature, the reaction rate is too low and the cooling is too 1D model, an unfeasible reactor length >20 m results in this
fast respectively, so that the equilibrium composition cannot case. For d > 6 cm, the worse heat transfer prevents appropri-
be maintained and at the reactor outlet temperature of 285 ◦ C ate cooling after the hot spot and accordingly the equilibrium
the equilibrium yield 98.3% is not attained. is shifted less than for smaller diameters. Besides the tube
A thorough parameter variation study concerning all pro- diameter, the total pressure and dilution of the catalyst were
cess and design variables has been performed to screen found to be sensitive parameters. For the chosen space veloc-
whether moderate hot spots can be kept up in a parametric ity the parameter variations point out that in the studied range
stable region to allow for high yields and stability likewise. it is not possible to operate the reactor in the parametric stable

800 700

600 600

400 500

400
300

300
280
0.0 0.5 1.0 0.00 0.25 0.50 0.75 1.00

Fig. 3 – Parametric sensitivity of the cooling temperature (dtube = 2 cm): (a) axial temperature profiles; (b) phase diagrams.
708 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712

region and to attain yields close to the equilibrium composi- basic understanding of characteristics for a CO2 methanation
tion for temperatures below 350 ◦ C. fixed-bed reactor the 1D model is evaluated as sufficient and
used exclusively in the following.
3.3. Comparison of the pseudo-homogeneous reactor
models 3.4. The heterogeneous reactor model

Next, it is studied how the different degree of detail in the three The focus of this section is laid on how transport processes
pseudo-homogeneous reactor models influences the model influence the reactor performance and how this can be used
predictions. The porosity for the 1D and the ˛W is chosen as beneficially in improving the reactor design. Fig. 6 shows the
the mean of the radial distribution of the (r)-model to ensure axial profiles for the temperature, the mole fractions and
comparability. As the three models reveal almost the identi- the overall effectiveness factor for methane formation at the
cal dependence of maximum temperature and yield on feed reference conditions and a feed temperature of 320 ◦ C. The
temperature for the reference case conditions (see Fig. S2 in maximum temperature difference in the catalyst pellet is
the supplementary), the feed is diluted with 50% of pure prod- below 6 ◦ C which is interpreted in terms of the onset of an
uct gas in order to be able to compare the models in detail. intraparticle diffusion limitation and the small Prater num-
This way, intermediate yields and conversions can be stud- ber (at the inlet conditions ˇ = 0.011), i.e. the heat removal is
ied since on the one hand the reaction rates are lower due to fast compared to the potential of heat release regarding the
the equilibrium and on the other hand the adiabatic temper- pellet scale. The temperature difference decreases from the
ature rise is less due to the lower concentration of reactants. beginning of the reactor toward the hot spot. This reflects the
Accordingly, maximum temperatures <550 ◦ C are found in the decrease of the carbon dioxide on the reactor scale as well
runaway region (Fig. 5). as the higher temperature level that shifts the equilibrium to
The maximum temperature in the 1D model is always larger carbon dioxide concentrations. In contrast, the maxi-
lower than in the two-dimensional models because it reflects mum temperature difference between the catalyst surface and
a radially averaged value. For calculating the effective heat the reactor level representing the gas phase temperature is
transfer coefficient a series of resistances has been considered located at the point of maximum effective reaction rate and
where the resistance due to radial dispersion is accounted for is significantly larger with a maximum value of 26 ◦ C. If the
via space velocity is reduced, the external heat transfer limita-
tion is more severe and the temperature difference can exceed
dtube
RDisp = . 100 ◦ C. This indicates that experimentally measured tempera-
8eff
r
tures reflecting the gas phase temperature do not necessarily
As pointed out for example by Finlayson (1974), this can be represent the maximum temperatures in the system which is
interpreted as a single-point collocation with the root of the in particular interesting concerning local catalyst deactivation
√
polynomial being located at r = 1/ 2 rtube where the value of a phenomena. The profiles of the mole fractions reveal a mass
parabolic function symmetric to r = 0 is equivalent to the radial transfer limitation in the beginning of the reactor where the
average. In addition, the radial dispersion of mass increases concentration of carbon dioxide decreases close to zero in the
the hot spot temperature. Thus, the runaway is found at higher pellet center. At the pore radius of 10 nm the transport is dom-
feed temperatures for the 1D model since the radial disper- inated by Knudsen diffusion. As a consequence of the lower
sion of mass is not accounted for and the reaction rate at the mean velocity of carbon dioxide compared to hydrogen the
average temperature r(T̄) is lower than the radially averaged transfer limitation is primarily caused by the diffusive flux of
reaction rate r(T) because of the exponential dependence on carbon dioxide. The gas composition in the bulk phase and on
temperature. To further improve the predictions of the 1D PFR the pellet surface is almost identical and for reasons of clarity
model, the maximum temperature in the tube center could not shown in the graph. Accordingly, external mass trans-
easily be approximated assuming a parabolic radial temper- port limitations are negligible under the conditions chosen.
ature profile. Also there are approaches to calculate a more The overall effectiveness factor for the formation of methane
appropriate radially averaged reaction rate, see for example (Fig. 6c) points out that despite of the excess temperature of
the ı-model by Koning et al. (2006). the catalyst pellets compared to the gas phase, mass transfer
The results concerning the runaway behavior for the 2D drastically slows down the reaction rates in the range of the
models are very similar among one another despite of devia- hot spot where the effectiveness factor is below 5%.
tions in the radial and also in the axial temperature profiles. The temperature profile in Fig. 6a itself indicates the influ-
The somewhat lower yields for the runaway region in the (r)- ence of the intraparticle mass transfer limitation on the
model reflect the maldistribution of the fluid flow after the maximum temperature. As the limitation slows down the
hot spot where the equilibrium is not attained anymore. The heat release due to chemical reaction, maximum tempera-
axial velocity is the highest in a region with a high porosity tures below 600 ◦ C can be realized now. In comparison to the
and accordingly a low volume-based reaction rate. Moreover, pseudo-homogeneous reactor model (see the phase diagrams
because of the vicinity to the tube wall, the temperature and in Fig. 6d), the temperature rise is not adiabatic anymore and
accordingly also the mass-based reaction rate are lowered the equilibrium is not attained in the hot spot. The range of
there. In total, the 1D PFR model reflects the main quali- the parametric sensitivity concerning the feed temperature is
tative trends while the 2D models might be necessary for accordingly shifted to higher values (Fig. 7). However, choos-
a quantitative evaluation and comparison to experimentally ing for example rpore = 50 nm and dp = 2 mm gives results fairly
determined profiles. The differences at the methanation of similar to the pseudo-homogeneous model. The intraparticle
the pure feed gas are less pronounced since distinct radial mass transfer hardly affects the reactor performance now and
temperature gradients, which are the main reason for devi- the maximum temperatures in the models differ by less than
ations, are not established without runaway of the reactor 40 ◦ C. This emphasizes that in the CO2 methanation process
where the equilibrium composition is attained anyway. For a there is potential for optimization concerning the interplay of
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712 709

600 1.0

0.8
500
0.6

400 α 0.4 α
Λ Λ
0.2

300
0.0
300 350 300 350

Fig. 5 – Maximum temperature and yield as a function of feed temperature in pseudo-homogeneous reactor models for the
diluted feed gas H2 /CO2 /CH4 /H2 O = 40/10/16.7/33.3 (dtube = 3 cm).

a b H2
gas phase
600 1.0 CO2
surface
pellet CH4
0.8 H2O
580 CO
500
0.6

0.4
400 560
0.2

0.0
0.0 0.5 1.0 0.0 0.5 1.0
z/L [-] z/L [-]
c d
1.0 heterogeneous
homogeneous
700
equilibrium
0.8

600
0.6
η

500
0.4

0.2 400

0.0
0.0 0.5 1.0 0.00 0.25 0.50 0.75 1.00
z/L [-] Ymethane [-]

Fig. 6 – Axial profiles of temperature (a), mole fraction (black: gas phase; gray: pellet center) (b), effectiveness factor of CH4
formation (c) and the phase diagram (d) for the heterogeneous reactor model (Tfeed = 320 ◦ C, dtube = 2 cm, dp = 5 mm,
dpore = 20 nm).

mass transport, reaction rates and heat transport on the pel-

800 let level also in terms of heat management and temperature
control on the reactor scale. In comparison to a dilution of the
catalyst with inert material, it is beneficial that the reaction
rates are slowed down exactly at the position where the heat
600 release needs to be limited while the reaction rates are less
affected in the cooling and low temperature region.

400 3.5. Temperature control in a fixed-bed membrane

reactor

This section addresses another option with respect to temper-

250 300 350 ature control besides optimizing transport properties of the
catalyst. Similarly, by controlling the gas composition on the
Fig. 7 – Comparison of the 1D pseudo-homogeneous and reactor level in every point of the reactor, the local adiabatic
heterogeneous reactor model (dtube = 2 cm, dp = 5 mm, temperature rise can be adjusted. One possibility is to feed the
dpore = 20 nm). components hydrogen and carbon dioxide separately into the
reactor and distribute one component appropriately. For this
purpose a fixed-bed membrane reactor might be suited ideally
710 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712

1.0
500

0.8
450 H2
0.6 CO2
CH4
400 0.4 H2O
annulus CO
inner tube 0.2
350

0.0
0.0 0.5 1.0 0.0 0.5 1.0
z/L [-] z/L [-]

Fig. 8 – Axial profiles of temperature and mole fraction for the fixed-bed membrane reactor (mcat = 0.7 kg, Q = 10.9 Nm3 /h,
d0 = 3.5 cm, di = 2 cm, p = 20 bar).

(see Scheme 2) where a component is fed via a central tube that equilibrium needs to be attained at temperatures well below
in a simple case is made of a porous steel membrane. The indi- 300 ◦ C where according to the kinetic model used here the
vidual feeding is possible in principle since in the power-to-gas activity is very low for yields >90%. This prevents to increase
concept hydrogen and carbon dioxide originate from different the GHSV which would be less problematic in terms of the
sources and do not need to be separated first. As Fig. 8 illus- high temperature region of the reactor.
trates, the temperature can be kept at values below 510 ◦ C, if • Finally, a fixed-bed membrane reactor has been modeled
the conditions are chosen adequately. In this example, a yield as an example for the capability of structured reactors.
of 91.7% is obtained for a reactor length of 80 cm and catalyst The separate feeding of the components enables for an
mass of 700 g at the same flow rate as in the reference case excellent temperature control and allows for attaining near-
which means that the equilibrium at the outlet temperature equilibrium gas compositions at elevated temperatures.
of 460 ◦ C is virtually attained (Yeq = 92.0). However, decreasing
the cooling temperature is not expedient since an accumula- Acknowledgments
tion of carbon dioxide in the beginning of the reactor has to be
prevented for controlling the adiabatic temperature rise. For Funding by the BMBF for the iC4 “Integrated carbon capture,
upgrading the product gas of the membrane reactor, a con- conversion and cycling” project is gratefully acknowledged.
ventional fixed-bed reactor of large diameter could be put in The authors appreciate support by the project partners E.ON,
series where the heat management now is simple since the Clariant, Linde, MAN and Wacker. D.S. acknowledges support
gas composition allows for almost isothermal operation. by the TUM Graduate School.

4. Conclusion Appendix A.

• Different pseudo-homogeneous reactor models were com- A.1. Calculation of the radial dispersion and effective wall
pared in order to assess the needed degree of detail for heat transfer coefficient for the 1D PFR and the 2D ˛W
modeling externally cooled fixed-bed reactors. Even the model
comparison at modest conversions showed that a simple
1D PFR model is capable of describing the qualitative trends The radial dispersion is split into a stagnant and a dynamic
and can be used for screening possible process conditions. contribution (Tsotsas, 2006b).
For quantitative evaluation and comparison to experimen-
tal results, however, in particular the 2D (r)-model allows eff  Pe
r
= bed + (A.1)
for a more detailed perspective. g g 8
• The comparison to results for a 1D heterogeneous reac-
tor model using the dusty-gas approach as particle model u0 g cp,m dp
Pe = (A.2)
showed that under specific conditions, i.e. large catalyst g
pellets, small pore radii and small Reynolds numbers,
severe intraparticle mass transfer and external heat trans- The stagnant contribution bed is a function of the conductiv-
fer limitations need to be considered. The results for the ity of the solid phase and of the gas phase as well as of the
heterogeneous model also emphasized the potential for porosity (Tsotsas, 2006a):
optimization on the pellet scale in terms of temperature
bed  
control. =1− 1− + 1 − kc (A.3)
• This modeling study highlighted the two key challenges g
for the CO2 methanation process: the reaction rates and
exothermicity in the first part of the reactor call for an  
2 B kp − 1 kp B+1 B−1
efficient heat removal if pure stoichiometric feed gas is kc = ln − −
N N2 kp B 2 N
converted without a product recycle or dilution by water
or methane. Tubular reactors of common diameters suffer
from a poor stability due to runaway under these condi- B p 1−
10/9
N=1− , kp = , B = 1.25
tions. The second challenge concerns the catalyst activity kp g
in the low temperature region. For a high quality SNG the
 chemical engineering research and design 9 2 ( 2 0 1 4 ) 702–712 711

For estimating the effective wall heat transfer coefficient for a ∂T {BP} 4
heat balance : (uctot )c̄p = UA,BP (T − TBP ) ∈ (A.8b)
fixed bed, the correlation by Martin and Nilles is used which ∂z di
similarly is based on a stagnant and a dynamic contribution
(Tsotsas, 2006b): Appendix B. Supplementary data
 
5 bed Supplementary data associated with this article can be found,
Nu = 1.3 + + 0.19Re0.75 Pr0.33 (A.4)
dtube /dp g in the online version, at doi:10.1016/j.cherd.2013.11.014.

˛W dP
Nu = (A.5) References
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