Article

pubs.acs.org/IECR

Effects of Catalyst Activity, Particle Size and Shape, and Process

Conditions on Catalyst Effectiveness and Methane Selectivity for
Fischer−Tropsch Reaction: A Modeling Study
Miloš Mandić,† Branislav Todić,† Ljiljana Ž ivanić,†,∥ Nikola Nikačević,‡ and Dragomir B. Bukur*,†,§
†
Chemical Engineering Program, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
‡
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, Belgrade 11000, Serbia
§
Artie McFerrin Department of Chemical Engineering, Texas A&M University, MS 3122, College Station, Texas 77843-3122, United
States

ABSTRACT: We investigate effects of catalyst activity, catalyst particle

shape (sphere, slab, and hollow cylinder), size (i.e., diffusion length),
catalyst distribution (uniform vs eggshell type distribution for a spherical
particle), and process conditions (temperature, pressure, syngas
composition, and conversion level) on catalyst effectiveness factor and
methane selectivity inside the catalyst pellet. In numerical simulations we
utilize kinetic parameters for CO consumption rate and CH4 formation
rate determined from experiments with a highly active Co/Re/γ-Al2O3
catalyst. It is found that the use of small spherical particles (0.2−0.5 mm)
or eggshell distribution for larger spherical particles with catalyst layer
thickness less than approximately 0.13 mm is needed to avoid negative
impact of diffusional limitations on CH4 selectivity under typical Fischer−
Tropsch synthesis operating conditions. For monolith reactors with wash-coated catalyst, diffusional limitations can be avoided
by using a catalyst layer thickness less than 0.11 mm at base case conditions (473 K, 25 bar, and H2/CO molar ratio of 2).

1. INTRODUCTION
Fischer−Tropsch synthesis (FTS) is a heterogeneous reaction
used to convert synthesis gas into a range of hydrocarbon
products. This reaction is a key step in the gas-to-liquid (GTL)
process in which natural gas is converted into liquid fuels and
value-added chemicals. Low-temperature FTS is conducted
commercially in two types of reactors: slurry bubble column
reactors and multitubular fixed bed reactors.1−3 The overall goal
of fixed bed reactor design is to maximize productivity and
selectivity to desired products (low methane and high selectivity
to liquid hydrocarbons−C5+ hydrocarbons) while minimizing
pressure drop and costs. To achieve these objectives, a judicious
choice for the catalyst particle size and shape, as well as process
conditions, is required. To avoid high pressure drop, the use of
relatively large particles (1−3 mm) is required,1,2 whereas to
achieve high productivity in a given reactor volume, one has to
use very active catalysts. These requirements lead to intraparticle
diffusional limitations resulting in lower reaction rate (decrease
in catalyst effectiveness) and decrease in selectivity to liquid
hydrocarbons.4−8 Slurry reactors utilize small catalyst particles
(less than 100 μm), and in this case, the intraparticle diffusional
limitations are not expected under normal operating conditions.
Microreactors for FTS have recently received a great deal of
attention because of increased heat removal at moderate pressure
drop.9,10 Several types of reactors have been considered for this
purpose, including (a) reactors with microstructured catalysts
(e.g., monoliths and foams), (b) coated microchannel reactors,
and (c) micro- and milli-fixed bed reactors in which small catalyst
particles are loaded into the packed bed.3 These types of reactors
in general minimize negative effects of intraparticle diffusional
limitations on activity and selectivity but are characterized by low
reactor productivity due to low amount of catalyst in the
reactor.11,12 The latter can be compensated by using highly active
FTS catalysts such as those developed by Oxford Catalysts
Group8,13 and milli-fixed bed reactors loaded with small particles.
The interplay between chemical reaction and intraparticle
diffusion for FTS applications (Co- and Fe-based catalysts) has
been studied in the literature either on a single-particle scale or as
a part of modeling of fixed bed reactors and has received
increased attention in recent years. In a majority of previous
studies a simplified kinetics (first-order in hydrogen or nth-order
in carbon monoxide) was utilized to calculate catalyst
effectiveness factor as a function of Thiele modulus, and
selectivity inside the particle was not considered.14−22 The first
quantitative analysis of chemical reaction with diffusion problem
for FTS reaction was published by Dixit and Tavlarides23 who
used a form of Langmuir−Hinshelwood (LH) kinetics derived
from experimental data with 0.5%Ru/γ-Al2O3 catalyst for FTS.24
This form of rate equation was later utilized by a number of
Received: January 5, 2017
Revised: February 20, 2017
Accepted: February 23, 2017
Published: February 23, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.iecr.7b00053

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research groups and became known as Yates and Satterfield
kinetics.25 Dixit and Tavlarides23 conducted a parametric study
(in terms of dimensionless parameters) to investigate the
relationship between the effectiveness factor (η) and Thiele
modulus (ϕ) and found that the η versus ϕ curve passes through
a maximum and can reach values exceeding 1. Also, they reported
that for some values of model parameters there exists a narrow
range of ϕ values over which multiple steady-state solutions are
possible. Selectivity aspects were not considered in this study.
Researchers at Exxon26−28 have introduced selectivity aspects
into mathematical modeling. Their model included continuity
equations for both fluid phase (plug flow reactor) and the catalyst
particle. Reaction rates for CO consumption and CH4 formation
were described by LH kinetics, and a separate model was used for
modeling hydrocarbon selectivity based on 1-olefin readsorption
concept. They found that selectivity of liquid-phase hydro-
carbons (C5+ hydrocarbons) increases initially with increase in
diffusional limitations due to diffusion-enhanced 1-olefin read-
sorption resulting in formation of high molecular weight
hydrocarbons and then begins to decrease because of diffusional
limitations by reactants, resulting in high H2/CO ratio inside the
pellet which favors chain termination reactions that favor lower
molecular weight hydrocarbons. To overcome these problems
and satisfy pressure drop requirements, Iglesia et al.4 utilized an
eggshell catalyst distribution where the catalyst is deposited only
in a thin layer near the outer surface of a relatively large particle. A
method of preparation of eggshell Co-based FTS catalysts was
described, and its beneficial effects on product selectivity were
illustrated with experimental data.
This type of analysis was carried one step further by Wang et
al.5 who utilized a comprehensive kinetic model for the catalyst
pellet in which both the overall syngas consumption and the
hydrocarbon product distribution are unified. This model was
developed from kinetic studies with Fe-based FTS catalyst29
which utilized the olefin readsorption concept. The advantages of
eggshell catalyst distribution on product distribution have been
investigated through numerical simulations.
A similar approach was used recently in analyzing performance
of a bench scale fixed bed reactor with Co-based FTS catalyst
(15%Co/γ-Al2O3).30 A comprehensive kinetic model of Todic et
al.31 was used in numerical simulations, which included a
continuity equation for the catalyst particle.
An alternative, and numerically significantly less demanding,
approach was used by Vervloet et al.7 to study the effect of
process conditions on catalyst effectiveness and C5+ productivity
and provide guidance for optimal reactor operation. The
interplay between reaction and diffusion in a single catalyst
particle was analyzed using the LH rate expression of Yates and
Satterfield25 for CO consumption rate and a variable chain
growth parameter (α) dependent on temperature and syngas
composition (H2/CO ratio). The same approach (the use of
Yates and Satterfield25 kinetic parameters and variable α
parameters from Vervloet et al.7) was used by Becker et al.6,32
as well as Gardezi and Joseph.33 There are some issues associated
with the approach used by Vervloet et al.7 Variation of α with
temperature and H2/CO ratio was determined from exper-
imental data of De Deugd34 for methane selectivity. Local α
values were calculated from reactant concentrations in the
particle, and average value of α was obtained by numerical
integration. Selectivities of C1−C4 and C5+ hydrocarbons were
then calculated assuming the ideal Anderson−Schulz−Flory
(ASF) distribution.28,35,36 However, it is well-known that actual
product distribution on Co FT catalysts deviates from the ideal
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ASF distribution. In particular, the actual CH4 selectivity is
significantly higher than that predicted from the ideal ASF
distribution; selectivity of C2 hydrocarbons is lower than
predicted value; and α varies with chain length.36−38 Thus,
predicted values of C5+ selectivity using the proposed approach
would not be very accurate. Also, the authors have used kinetic
parameters for syngas consumption from Yates and Satterfield25
experimental data with a catalyst different than the catalyst used
to obtain the expression for variation of α with temperature and
syngas composition. In general, one should use kinetic
parameters for activity and product distribution obtained from
an experimental study with the same catalyst.
In this study we investigate effects of particle shape (sphere,
slab, and hollow cylinder), size (i.e., diffusion length), catalyst
distribution (uniform vs eggshell type distribution for a spherical
particle), and process conditions (temperature, pressure, syngas
composition, and conversion level) on catalyst effectiveness
factor and methane selectivity inside a particle. In numerical
simulations we utilize kinetic parameters for CO consumption
rate and CH4 formation rate determined from experiments with a
highly active Co/Re/γ-Al2O3 catalyst, which is more representa-
tive of current Co-based catalysts used in industrial applications
than the catalyst used by Yates and Satterfield.25 Models of
diffusion−reaction interaction are helpful in determining an
optimal catalyst layer thickness that maximizes catalyst
effectiveness and improves FTS product selectivity and provide
guidance for catalyst design and choice of process conditions.
2. MODEL DESCRIPTION
The overall stoichiometry of FTS on cobalt catalyst was
described by the following equation:
CO + (13/6)H 2 = H 2O + (1/6)C6H14 (1)
which is representative of an average molecular weight of
hydrocarbons produced and H2/CO consumption ratio for
experiments with 0.48%Re−25%Co/Al2O3 catalyst.31 In general,
H2/CO consumption ratio varies with product selectivity and lies
between 2 (production of very long chain molecules, α = 1) and 3
(production of CH4 from syngas).
It is assumed that the catalyst particle is filled with high
molecular weight hydrocarbons (wax) and that external mass-
and heat-transfer resistances are negligible, so that concen-
trations of species and temperature at the particle surface are the
same as those in the bulk. The reactants and products are
dissolved in wax at the surface and throughout the particle. For
steady-state conditions, assuming Fick’s law of diffusion and
isothermal pellet, the general reaction−diffusion continuity
equation is given as
1 d ⎛ g dyi ⎞
· ⎜x · ⎟ + υi ·(ϕ′i )2 ·R̅ CO = 0
x g dx ⎝ dx ⎠ (2)
where x is the dimensionless distance and superscript g stands for
geometry (g = 2, 1, and 0 for sphere, cylinder and slab,
respectively); yi (Csi /CsCO) is dimensionless concentration (i =
CO, H2, H2O, and n-hexane), νi stoichiometric coefficient (νi =
−1, −13/6, 1, and 1/6 for CO, H2, H2O, and n-hexane,
respectively), R̅ CO the dimensionless CO consumption rate
(R C O /R Cs O ), and ϕ′ i the dimensionless parameter
s
ρp ·(−R CO)
(ϕ′i = Lg ). This parameter includes catalyst density
s
De ,i ·CCO
(ρp), geometric characteristic length (Lg), surface concentration
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of CO (CsCO) in the liquid medium, and effective diffusivity dyi

x = 0 (sphere or slab): =0
coefficient of species i (De,i). dx (2b)
The assumption of uniform temperature distribution in a
pellet (isothermal conditions) was verified by numerical solution x = ri /ro (hollow cylinder): yi = C is/CCO
s
(2c)
of mass and energy balance equations under a conservative set of
conditions to maximize temperature gradients inside the pellet: dyi
relatively large spherical particle (dp = 4 mm); low value of x = 1 − δ /R (eggshell distribution): =0
dx (2d)
effective thermal conductivity, keff = 0.1 W/(m·K); and high
value of heat of reaction, −173 kJ/mol. It was found that the 2.1. Kinetics. CO consumption rate per unit mass of catalyst
maximum temperature difference in the particle is 0.15 K, which is described by LH kinetics:23,25
has no impact on concentration profiles, effective diffusivity, and
k·PCO·PH2
CH4 selectivity. Vervloet et al.7 reached the same conclusion by ( −R CO) =
using relevant dimensionless groups for estimation of the (1 + a ·PCO)2 (3)
maximum ΔT in a pellet.
The second-order differential equation (eq 2) was solved for Numerical values of kinetic rate constant (k) and adsorption
several particle shapes (sphere with uniform catalyst distribution constant (a) have been reported by Yates and Satterfield25 at two
and eggshell catalyst distribution, flat plate, and hollow cylinder), temperatures (220 and 240 °C) from regression of experimental
as shown in Figure 1. The geometric characteristic length (Lg) for data with 21.4% Co/3.9% Mg/SiO2 catalyst, which will be
referred to as YS catalyst. Maretto and Krishna39 estimated
activation energy and adsorption enthalpy of k and a for YS
catalyst. Temperature dependence for these two parameters is
given by the following equations:
⎡ ⎛ 1 1 ⎞⎤
k(T ) = 8.8533 × 10−3· exp⎢4494.41⎜ − ⎟⎥
⎣ ⎝ 493.15 T ⎠⎦
mol/(s kgcat bar 2) (4)

⎡ ⎛ 1 1 ⎞⎤
a(T ) = 2.226· exp⎢ − 8236⎜ − ⎟⎥1/bar
⎣ ⎝ 493.15 T ⎠⎦ (5)

It should be noted that Yates and Satterfield25 and Maretto and

Figure 1. Representation of particle shapes and dimensions: (a)
spherical particle with uniform catalyst distribution, (b) spherical
particle with eggshell catalyst distribution, (c) hollow cylinder particle,
and (d) slab (flat plate).
each particle shape is as follows: radius (R) for a sphere, outer
radius (ro) for a hollow cylinder, and thickness (L) for a slab (flat
plate). Dimensionless distance x, in eq 2, for different pellet
shapes is x = r/R (sphere), x = r/ro (hollow cylinder), or x = z/L
(slab).
Dirichlet boundary conditions are used for surfaces exposed to
the surrounding fluid (x = 1), and Neumann (zero flux)
conditions are used at x = 0 (sphere with uniform catalyst
distribution and slab) or at x = 1 − δ/R (eggshell distribution in a
spherical particle):
x = 1 (outer surface of the particle, all four geometries): yi = C is/CCO
s
(2a)
Krishna39 obtained numerical values of k and a from data for
syngas (H2 + CO) consumption rate rather than CO
consumption rate. It appears that several research groups used
eq 4 as the rate constant for CO consumption rate,6,7,33 without
correction for stoichiometry, in modeling the reaction with
diffusion in a single particle.
We have estimated parameters k and a in eq 3 from
experimental data with a catalyst synthesized at Center for
Applied Energy Research (CAER) at the University of Kentucky
having composition 0.48%Re−25%Co/Al2O3. Experimental
data used to estimate kinetic parameters can be found in Table
1 of Todic et al.37 Numerical values of kinetic parameters used in
simulations for both CAER and YS catalysts are summarized in
Table 1. Numerical value of k in eq 4 for YS catalyst was divided
by (1 + 13/6) to the obtain rate constant for CO consumption. It
is worth noting that CAER catalyst is an order of magnitude more
active under typical FTS operating conditions compared to the
YS catalyst,25 and as such is more representative of modern Co
catalysts used in industrial applications.
The key aspect of FTS catalyst selectivity is methane
selectivity. It is the most undesirable product, and reduction in
the amount of methane is of utmost importance. Methane
formation rate was calculated using a recently proposed
expression:40

Table 1. Kinetic Parameters for Rate of CO Disappearance According to Equation 3

Yates and Satterfield (YS) CAER

catalyst 21.4% Co/3.9% Mg/SiO2 25% Co/0.48% Re/Al2O3
k (mol/(s·kg·bar2)) 26·exp(−4494.4/T) 4.2 × 105·exp(−8742/T)
a (1/bar) 1.24 × 10−7·exp(8236/T) 6.45 × 10−2·exp(1295.3/T)

C DOI: 10.1021/acs.iecr.7b00053
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aM bM Table 2. Reaction Conditions and Parameters Used in

R CH4 = kM PCOP H2 /(1 + mM ·PH2O/PH2) (6)
Numerical Simulations
kM = AM e−EM / R gT (6a) description symbol value ref
temperature T 473−493 K
where numerical values of kinetic parameters were estimated
pressure P 20−30 bar
from the same set of experimental data as those in eq 3 (Table 1
syngas ratio in the bulk H2/CO 1.4−2.0
of Todic et al.37). Estimated values of numerical parameters in eq
catalyst porosity ε 0.5
6 are aM = −0.99, bM = 1.28, mM = 0.58, AM = 2.25 × 1011 (mol/
catalyst tortuosity τ 2
(kg·s·bar0.29)), and EM = 140 (kJ/mol).
catalyst particle density ρp 1200 kg m−3
Substituting numerical values for constants aM, bM, and mM catalyst particle diameter dp 0.085−4 mm
into eq 6, we obtain the following expression for CH4 formation catalyst layer thickness (slab) L 0.035−0.300 mm
rate: eggshell layer thickness δ 0.075−0.300 mm
kM(T) ·(PH2 /PCO)0.99 ·PH2 0.29 CO diffusivity in wax Dwax,CO (1.24−1.44) × 10−8 m2 s−1 50
R CH4 = (mol/(kg·s)) H2 diffusivity in wax Dwax,H2 (3.13−3.62) × 10−8 m2 s−1 50
1 + 0.58·(PH2O/PH2) (7) H2O diffusivity in wax Dwax,H2O (2.10−2.42) × 10−8 m2 s−1 50
Equation 7 predicts that CH4 formation rate increases with C6H14 diffusivity in wax Dwax,C6H14 (5.12−5.98) × 10−9 m2 s−1 50
temperature, partial pressure of H2, and H2/CO ratio and is Henry’s coefficient for CO HCO 345.1−356.6 bar 53
inhibited by partial pressure of water. The inhibiting effect of Henry’s coefficient for H2 HH2 442.3−472.6 bar 53
water on CH4 selectivity is well-established from studies with Henry’s coefficient for H2O HH2O 41.9−49.3 bar 53
both indigenous and externally added water,40−47 whereas the Henry’s coefficient for C6H14 HC6H14 9.88−12.3 bar 53
underlying causes for this behavior are still not completely
density of wax (n-octacosane) ρw 678.1−691.4 kg m−3 50
understood.41,48,49
2.2. Physical Properties. We consider the case in which the
catalyst particle is completely filled with hydrocarbon wax, the For normal reactions (rate decreases as conversion increases),
physical properties of which are assumed to be those of n- the effectiveness factor is ≤1, and is a measure of utilization of
octacosane (C28H58). Diffusivities of species in wax were catalyst volume for reaction. However, in our case, the CO
estimated from Akgerman’s correlation.50,51 This correlation reaction rate (eq 3) passes through a maximum before it starts
has been used previously,6,21 and its predictions are similar to decreasing with decrease in reactant concentrations, and it is
those obtained using correlations of Wang et al.5 and possible to have η > 1 for some conditions.
Makrodimitri et al.52 Solution of eq 2 provides partial pressures needed to evaluate
The effective diffusivity of the component was calculated from methane formation rate (eq 7) and calculate local methane
selectivity at any point inside the catalyst as
ε
De,i = Dwax,i R CH4
τ (8) SCH4 = ·100%
( −R CO) (11)
where ε is particle porosity and τ is tortuosity factor.
Henry’s law constants for reactants and products in n- which is valid for Co catalysts because of their low water gas shift
octacosane were calculated from Marano and Holder’s activity, i.e., low CO2 formation.
correlation.53 This correlation is based on experimental data Then, average CH4 selectivity can be obtained by integration
with fluids (different types of FTS waxes and high molecular of local reaction rates as follows:
weight hydrocarbons) and process conditions (temperature and V V
1 1
pressure) that are typical for FTS (Marano54). Liquid-phase SCH
̅ 4=
V
· ∫0 ρp R CH4 dV / ·
V
∫0 ρp ( −R CO)dV
concentration of a species i is related to partial pressure of i via
V
Henry’s law constant ∫0 R CH4 dV
=
Pi = Hi(C i /C L) (9) V
∫0 (−R CO)dV (12)
where Ci is molar concentration of species i (mol/m3), CL the
total liquid-phase concentration (mol/m3), Pi partial pressure It should be noted that CH4 formation rate (eq 7) is not
(bar), and Hi Henry’s law constant (bar). bounded, and for large H2/CO ratios it can assume a very high
The parameter values used in model simulations are value. Also, as the CO gets depleted inside the particle, RCO
summarized in Table 2. approaches zero. If either one or both of these two possibilities
2.3. Catalyst Performance Indicators. Catalyst efficiency occur, the local CH4 selectivity would tend to infinity, whereas its
and CH4 selectivity are the two key factors describing catalyst value physically cannot exceed 100%, i.e., CH4 formation rate
performance. The efficiency is expressed in terms of effectiveness cannot exceed CO consumption rate (RCH4 ≤ (−RCO)). Thus, if
factor, which represents a ratio of average reaction rate in the at some point in the pellet it is found that RCH4 > (−RCO), the
pellet divided by rate at the surface conditions: condition RCH4 = (−RCO) is imposed in calculation of local and
V average CH4 selectivities (eqs 11 and 12) from this point onward.
∫0 (−R CO)ρp dV 2.4. Numerical Methods. Solution was obtained using
η= s
V ·( −R CO)ρp (10) Matlab’s bvp4c function, which is used to solve boundary value
problems for ordinary differential equations. The function uses
where V represents the volume of the region in which the catalyst finite difference method, which implements a colocation formula.
is located. For each component, eq 2 was written as a system of two first-
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Figure 2. Effect of catalyst activity (CAER vs YS catalyst) on (a) CO and H2 concentration, (b) H2/CO ratio, (c) CO reaction rate, and (d) local CH4
selectivity (CAER catalyst). Conditions: dp = 2 mm, T = 473 K, P = 25 bar, XCO = 0%, and H2/CO = 2.
order differential equations, resulting in a system of eight first-
order differential equations with conditions specified at two
different points. Spacing between grid points was not fixed
because of the nature of bvp4c algorithm, because the method
iteratively adjusts spacing in order to achieve convergence
tolerance. Initial guesses used depended on expected profiles.
For conditions which would result in small values of ϕ′i (low
diffusional limitations), boundary conditions on the surface were
taken as initial guesses for all points, while for larger ϕ′i
conditions, guesses were chosen by trial and error.
Local CH4 selectivity was calculated algebraically using
previously calculated concentration profiles of CO, H2, and
H2O. Average CH4 selectivity and effectiveness factor were
calculated using trapezoidal rule (Matalab’s function trapz). This
method is accurate enough because of the high density of mesh
over which the integration is done.
3. RESULTS AND DISCUSSION
Even though the governing differential equations were solved
numerically in their dimensionless form, we present results in
terms of dimensional variables to facilitate better physical
understanding and relate them to previous studies and industrial
applications.
3.1. Effect of Catalyst Activity. Results from simulations
with CAER catalyst (high-activity catalyst) and YS catalyst (low-
activity catalyst) are shown in Figure 2 for conditions typical of
industrial practice (473 K, 25 bar, H2/CO ratio of 2). Simulations
are for a spherical particle 2 mm in diameter, which is
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representative of sizes (1−3 mm) used in industrial reactors to
avoid a high pressure drop.1,2,4 Results are shown for conditions
near the reactor inlet where the CO conversion is very small (XCO
= 0%). These conditions are the least favorable for achieving low
methane selectivity because of the absence of water at the particle
surface.
Steep gradients are observed for reactant liquid-phase
concentrations in the case of CAER catalyst, whereas
concentrations decrease slowly for YS catalyst. For CAER
catalyst, the concentration of CO approaches zero at
approximately 0.2 mm from the particle surface (Figure 2a)
because of lower rate of diffusion of CO compared to H2. This in
turn causes very rapid increase in H2/CO ratio inside the particle
(Figure 2b). We show results only up to H2/CO = 20, but this
ratio tends to infinity deeper inside the particle. On the other
hand, H2/CO ratio for the YS catalyst increases slightly from 2 at
the surface of the particle to ∼2.4 at the center.
CO consumption rate for the CAER catalyst increases rapidly
in the region near the surface to reach a maximum value at
approximately 0.11 mm from the surface and then decreases to
essentially zero value at about 0.27 mm from the surface (Figure
2c). This behavior is caused by change in effective reaction order
from negative at high CO concentration to positive at low CO
concentrations (see eq 3). For YS catalyst, the CO consumption
rate increases slightly from the surface to the center of the
particle, which is consistent with moderate decrease in CO
concentration shown in Figure 1a. It is important to note the
difference in scale for the two ordinate axis. Consumption rate of
CO is much lower with the YS catalyst relative to the CAER
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Figure 3. Effect of particle size on (a) CO concentration, (b) H2/CO ratio, (c) CO reaction rate, and (d) local CH4 selectivity. Conditions: T = 473 K, P
= 25 bar, XCO = 0%, and H2/CO = 2.
catalyst. The ratio of reaction rates (CAER/YS) at the catalyst
surface for these process conditions is 36. Observed differences in
concentration profiles and H2/CO ratios with the two catalysts
are caused by respective differences in the catalyst activity.
Intraparticle diffusional limitations are much stronger with the
more active catalyst.
Local CH4 selectivity (Figure 2d) increases exponentially,
mirroring trends in H2/CO ratio (Figure 2b), and reaches 100%
at approximately 0.16 mm from the surface. This is in accordance
with the rate equation for CH4 formation (eq 7), which predicts
increase in rate with increase in H2/CO ratio, and the definition
of local selectivity, which has the rate of CO disappearance in the
denominator (eq 11). The calculated value of local CH4
selectivity tends to infinity with increasing distance from the
surface of the particle, but physically selectivity cannot exceed
100%; this is shown as a broken horizontal line in Figure 2d. We
do not have rate parameters for CH4 formation for the YS
catalyst; thus, there are no results for local CH4 selectivity for this
catalyst.
The catalyst effectiveness values are 0.52 (CAER) and 1.05
(YS), whereas the average CH4 selectivity, calculated from eq 12,
for CAER catalyst is 19.4%. The latter clearly indicates a negative
impact of intraparticle diffusional resistance on the catalyst
performance (high CH4 and consequently low C5+ selectivity).
Simulations were performed for these process conditions and
particle size for external conditions corresponding to location in a
reactor where CO conversion is 50%. Liquid-phase concen-
trations of species (reactants and products) at the catalyst surface
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were calculated assuming reaction stoichiometry described by eq
1. Calculated values of the effectiveness factor were 0.46 (CAER)
and 1.06 (YS), whereas CH4 selectivity was 13.8%. Initial (at the
surface) reaction rates are higher when XCO = 0%, but the impact
on effectiveness factor is small, whereas CH4 selectivity is
significantly lower when XCO = 50%. The latter is due to the fact
that water is present at the outer surface and it inhibits CH4
formation rate (see eq 7). However, the calculated value of CH4
selectivity is too high for industrial applications.
The above results show that the use of YS rate equation with
original parameter values obtained from experiments with Co/
Mg/SiO2 catalyst25 underestimates the extent of diffusional
resistance in the case of more active Co FTS catalysts. Some
researchers7,8 have simply multiplied YS rate by a constant value
(up to 10) to simulate performance of more active catalysts, but
this approach does not account correctly for variation of rate with
temperature and pressure. The ratio of reaction rates (CAER/YS
catalyst) at the surface is a function of process conditions, and it
varied between 14.9 (at 493 K, 20 bar, and XCO = 50%) and 37 (at
473 K, 30 bar, and XCO = 0%). For each catalyst, one needs to
determine the correct values of activation energy and enthalpy of
adsorption experimentally, as well as reaction orders with respect
to reactants. In the remaining sections of this paper we present
results using kinetic parameter values for CAER catalyst.
3.2. Effect of Particle Size. Although the use of small
particles (less than 1 mm) is not feasible for a large-scale
industrial fixed bed reactors because of excessive pressure drop,
this is not as significant constraint for microchannel structures
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Figure 4. Effect of catalyst shape and catalyst distribution on (a) CO concentration, (b) H2/CO ratio, (c) CO reaction rate, and (d) local CH4 selectivity.
Conditions: L = δ = ro − ri = 0.15 mm, T = 473 K, P = 25 bar, XCO = 0%, and H2/CO = 2.
which utilize shorter lengths. The use of small particles decreases
intraparticle transport resistances, which is essential for
maintaining low CH4 selectivity. Results of simulations (CAER
catalyst) with small spherical particles (0.2, 0.4, and 0.6 mm) and
comparison with a 2 mm spherical particle are shown in Figure 3.
As expected, the CO concentration profile becomes steeper as
the particle size increases (Figure 3a). H2/CO ratio (Figure 3b)
for smaller particles (0.2 and 0.4 mm in diameter) is close to the
bulk ratio of 2, whereas it increases rapidly for larger particles (0.6
and 2 mm). CO consumption rate increases gradually from the
surface to the center for the smaller particles (Figure 3c) because
of reduction in rate inhibition by CO. For larger particles, CO
consumption rate passes through a maximum and then
decreases. For dp = 0.6 mm, the reaction rate at the center of
the pellet is about one-third of the rate at the surface, whereas for
the largest particle (dp = 2 mm), the CO rate approaches zero at
approximately 0.27 mm from the surface, and a large fraction of
the particle volume is not utilized for reaction. Local methane
selectivity increases with distance from the surface, but the
increase is small for two small particles (0.2 and 0.4 mm) and
very rapid for the larger particles (0.6 and 2 mm). In the latter
case, local selectivity reaches 100% at 0.23 mm for 0.6 mm
particle and at 0.16 mm for 2 mm particle (Figure 3d).
Effectiveness factor values are 1.01 (0.2 mm), 1.04 (0.4 mm),
1.12 (0.6 mm), and 0.52 (2 mm), whereas the corresponding
average values of CH4 selectivity are 5.6, 5.7, 7.6, and 19.4%,
respectively.
G DOI: 10.1021/acs.iecr.7b00053
Article
For a given set of conditions (473 K, 25 bar, H2/CO = 2, and
XCO = 0%) the use of spherical particle of 0.4 mm in diameter
would be an optimal choice because it results in high
effectiveness factor and low CH4 selectivity. Compared to the
0.2 mm particle, increased diffusional resistance is beneficial in
that it gives a slightly higher effectiveness factor without an
adverse effect on CH4 selectivity. The use of 0.4 mm particles in
microchannel structure may be an upper limit for channels up to
about 5 mm, whereas a smaller particle size would be preferable
for smaller channels. The use of larger particle 0.6 mm in
diameter results in even higher effectiveness factor, but CH4
selectivity is higher than with the two smaller particles, which
makes it less suitable for commercial applications.
3.3. Effects of Particle Shape and Catalyst Distribution.
One way to minimize negative impact of intraparticle diffusional
limitations on hydrocarbon selectivity (high CH4 and low C5+
selectivity) while maintaining pressure drop requirements is to
use eggshell catalyst distribution where cobalt is located near the
outer pellet surface.4,33,55−57
Reduction in diffusion length can also be accomplished using
wall coated monolith reactors for FTS reaction, and this has
received considerable attention in recent years.12,58−62 This
geometry can be approximated by that of an insulated slab (flat
plate). Another way to minimize diffusion path of reactants is to
utilize hollow cylinder particles of small thickness.
Figure 4 shows results of simulations with these three
geometric shapes (slab/plate, hollow cylinder, and sphere with
eggshell distribution) having the same catalyst layer thickness of
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Industrial & Engineering Chemistry Research Article

Table 3. Effect of Process Conditions on Effectiveness Factor and Average Methane Selectivity of a Spherical Catalyst Particle
effect of process conditions P (bar) T (K) H2/CO (−) XCO (%) η (−) S̅CH4 (%) ϕCOa (−)
dp = 0.4 mm effect of pressure 20 473 2 0 1.042 5.71 0.56
30 473 2 0 1.041 5.71 0.48
effect of temperature 25 473 2 0 1.042 5.67 0.52
25 493 2 0 1.112 12.7 0.76
effect of syngas ratio 25 473 2 0 1.042 5.67 0.52
25 473 1.7 0 1.016 5.39 0.46
25 473 1.4 0 1.001 5.13 0.39
effect of CO conversion 25 473 2 0 1.042 5.67 0.52
25 473 2 25 1.036 5.05 0.53
25 473 2 50 1.020 4.08 0.55
dp = 2 mm effect of pressure 20 473 2 0 0.458 19.8 2.81
30 473 2 0 0.563 18.9 2.40
effect of temperature 25 473 2 0 0.516 19.4 2.58
25 493 2 0 0.355 28.3 3.82
effect of syngas ratio 25 473 2 0 0.516 19.4 2.58
25 473 1.7 0 0.552 16.4 2.28
25 473 1.4 0 0.586 11.8 1.97
effect of CO conversion 25 473 2 0 0.516 19.4 2.58
25 473 2 50 0.455 13.8 2.75
a
ϕCO defined by eq 13.

0.15 mm (L = δ = ro − ri = 0.15 mm in Figure 1, and ro = R = 1
mm). CO concentration declines monotonically with distance
from the surface for slab and eggshell catalysts, whereas it passes
through a minimum at approximately 0.075 mm for a hollow
cylinder (Figure 4a). The observed trend for the latter is the
consequence of the fact that a hollow cylinder has two surfaces
exposed to the surrounding fluid, whereas the slab and the
particle with the eggshell catalyst distribution have only one
surface exposed to the fluid. The steepest gradient is observed
with the slab layer, followed by the eggshell layer. As a result of
differences in diffusion rates of H2 and CO in the particle, the H2/
CO ratio increases with the distance from the surface, with a
trend opposite to that of CO concentration (Figure 4b). Internal
H2/CO ratios for the slab and eggshell layer are appreciably
higher than those at the surface, whereas this ratio is relatively
constant for the hollow cylinder. Local CH4 selectivity follows
the same qualitative trend as the H2/CO ratio (Figure 4c). We
see from these data that intraparticle diffusional resistance
increases in the following order: hollow cylinder < eggshell layer
< slab, which is consistent with the order of increasing effective
diffusional path (Lc = V/S) for these three geometries. Even
though these three geometries have the same catalyst layer
thickness, the corresponding effective diffusional paths are
different.
Effectiveness factor values are 1.216 (slab), 1.171 (eggshell),
and 1.024 (hollow cylinder). As seen above for small spherical
particles, a moderate intraparticle diffusional resistance results in
higher effectiveness factor due to reduction in rate inhibition by
CO (negative reaction order kinetics). However, CH4 selectivity
is adversely affected by diffusional limitations because of increase
in H2/CO ratio inside the pellet, and the average values of CH4
selectivity are 7.90% (slab), 6.53% (eggshell), and 5.62% (hollow
cylinder). In this case, the hollow cylinder pellet would be the
best choice from the performance perspective; however, it would
not be suitable for industrial applications because of low
mechanical strength. To avoid diffusional limitations in wall
coated monolith reactors using CAER catalyst at these
conditions (473 K, 25 bar, H2/CO = 2, XCO = 0%), one would
need to use layers with thickness less than 0.11 mm, whereas the
H DOI: 10.1021/acs.iecr.7b00053
eggshell thickness should be less than about 0.13 mm (see
section 3.5).
Several research groups have reported that low CH4 selectivity,
comparable to that of powder catalysts, can be obtained with
monolith reactors having layer thickness less than 0.05 mm.12,58
This is much more conservative than the estimated value for
CAER catalyst at base case conditions. Iglesia et al.4 used eggshell
catalyst distribution (thickness 0.1−0.2 mm) with spherical
particles 2.2 mm in diameter at 473 K, 20 bar, H2/CO = 2.1, and
CO conversion of 50−60%, whereas Fratalocchi et al.56 reported
that eggshell catalyst with 0.075 mm thickness (0.6 mm particle
diameter) has the same CH4 selectivity and slightly higher C5+
selectivity than that of the powder catalyst (0.075−0.10 mm
diameter) at 503 K, 25 bar, and H2/CO = 1.7 and CO
conversions between 34 and 42%. Our estimate is in good
agreement with values reported by Iglesia et al.4 under similar
reaction conditions and with a similar particle size, whereas
Fratalocchi et al.56 reported smaller thickness but at significantly
higher reaction temperature and with a smaller overall particle
size.
3.4. Effect of Process Conditions. Effect of process
conditions (pressure, temperature, syngas ratio on the surface,
and CO conversion level) on effectiveness factor and methane
selectivity of CAER catalyst is summarized in Table 3 for two
spherical particles with diameters of 0.4 mm and 2 mm. We
found (section 3.2) that the use of a small particle (0.4 mm)
results in negligible diffusional limitations at the baseline
conditions (473 K, 25 bar, H2/CO = 2, and XCO = 0%), whereas
pore diffusion has a strong effect on catalyst performance in the
case of the 2 mm particle. Results shown with these two particle
sizes show influence of process conditions in kinetic regime (dp =
0.4 mm) and pore diffusion regime (dp = 2 mm).
Change of total pressure from 20 to 30 bar has a negligible
effect on η and SC̅ H4 for the small particle, whereas for 2 mm, the
increase in pressure results in a small increase in η and a small
decrease in S̅CH4, which is due to decrease in the value of the
Thiele modulus.
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Industrial & Engineering Chemistry Research Article

Increase in temperature from 473 to 493 K results in 7%

increase in the value of η and significant increase in methane
selectivity (from 5.67 to 12.7%) for dp = 0.4 mm, whereas in the
region of pore diffusion control (dp = 2 mm), η decreases and
S̅CH4 increases because of increase in diffusional resistance
(higher value of ϕCO).
Effect of syngas ratio changes on η is relatively small, but
decrease in the H2/CO ratio results in reduction of SC̅ H4 for both
particle sizes. The effect on S̅CH4 is more pronounced in the case
of larger particles.
Vervloet et al.7 have shown through model simulations and
optimization that space-time-yield of C5+ hydrocarbons can be
significantly improved relative to typical conditions of T = 500 K,
P = 30 bar, and H2/CO = 2 by increasing reaction temperature to
530 K and pressure to 36 bar while simultaneously decreasing
bulk H2/CO ratio to 1. Robota et al.8 showed CO, H2, and H2/
CO profiles for different bulk H2/CO ratios ranging from 0.5 to
1.8 for a 0.25 mm diameter particle at 478 K and 24 bar using the
YS rate equation with scaling factor of 10. For H2/CO bulk ratios
less than 0.9, the internal H2/CO ratio decreases slightly from the
surface to the center of the particles, whereas for bulk ratios
greater than 1.1, the ratio increases with distance from the
surface.
It is clear from eq 7 that the rate of CH4 formation will
decrease with decreasing H2/CO ratio; however, it is known that
one of the mechanisms for catalyst deactivation is carbon
deposition,63−65 and operation at low H2/CO ratios would
accelerate the rate of deactivation. Therefore, it is not clear
whether lowering of H2/CO feed ratio would be a feasible
method of controlling CH4 selectivity under diffusion limited Figure 5. Effectiveness factor as a function of Thiele modulus. (a) Slab,
conditions. sphere, eggshell and hollow cylinder particle (range of conditions: T =
473−493 K, P = 20−30 bar, CAER and YS catalyst, XCO = 0−50%, dp =
As the conversion along the reactor increases, the concen- 0.085−4 mm, L = 0.035−0.300 mm, δ = 0.075−0.300 mm, ro − ri =
tration of water outside the catalyst particle increases, and this 0.150−0.500 mm). (b) Spherical particle (CAER catalyst, range of
has significant effect on CH4 selectivity. The effect of CO conditions: T = 473−493 K, P = 20−30 bar, XCO = 0−50%, dp = 0.085−4
conversion on η is small with both particles because the value of mm).
the Thiele modulus does not change much with conversion (0−
50% range). However, significant reductions in S̅CH4 were Results in Figure 5a show η versus ϕ data for all shapes, sizes,
observed as conversion increases from 0% (reactor inlet) to 50% and process conditions investigated except for data correspond-
because of increase in water concentration, which inhibits ing to H2/CO ratios of 1.4 and 1.7. These data are excluded
methane formation rate (see eq 7). because the H2/CO ratio has effect on both boundary condition
3.5. Effectiveness Factor and Methane Selectivity as a (eq 2a) for H2, as well as on dimensionless reaction rate in the
Function of Generalized Thiele Modulus. Results from differential equation (eq 1). Changes in total pressure have no
simulations with different particle shapes (sphere, slab, hollow effect on the boundary conditions and have a small effect on
cylinder), different sizes (sphere with diameters ranging from reaction rate for the range of pressures investigated (20−30 bar);
0.085 mm to 4 mm, catalyst layers of different thicknesses thus, data for all pressures in this range are shown in Figure 5a.
ranging from 0.035 mm to 0.5 mm), form of catalyst distribution Temperature has a small effect on the boundary condition (eq
(uniform and eggshell), and process conditions (T = 473−493 K, 2a) for H2 (through variation of solubility with temperature), and
P = 20−30 bar, H2/CO = 1.4−2) are shown in Figures 5 and 6. dimensionless reaction rate is not very sensitive to temperature
Abscissa values represent generalized Thiele modulus based (473−493 K) at a constant value of ϕ. Therefore, data at both
on characteristic length for diffusion (Lc = V/S) as proposed by temperatures (473 and 493 K) are included. The largest scatter of
Aris.66 The formula for generalized Thiele modulus is points occurs in the region 0.7 < ϕ < 1, because different shapes
have different values of η at similar values of ϕ, and differences in
ρp ·( −R COs) kinetic parameters (CAER vs YS catalyst) have impact on results
ϕ = ϕCO = Lc s
De,CO·CCO in this range of ϕ values. In general, values of η for spherical
(13)
particles become greater than 1.06 in the region 0.7 < ϕ < 1,
where Lc = V/S (V = volume in which the catalyst is located; S = whereas for other shapes this takes place at higher values of ϕ
surface area exposed to surrounding fluid). (0.99 < ϕ < 1.26). For ϕ values less than about 0.6, η ≈ 1 (1−
Characteristic diffusion lengths for different pellet shapes and 1.06), which is the region of kinetic control, whereas for ϕ > 1.6,
forms of catalyst distribution as shown in Figure 1 are as follows: the effectiveness factor decreases with increasing ϕ and is less
Lc = R/3 (sphere with uniform catalyst distribution), Lc = (R/3)· than 1 for all particle shapes. This is the region where
[1 − (1 − δ/R)3] (sphere with eggshell catalyst distribution), Lc intraparticle diffusional resistance becomes increasingly impor-
= (ro − ri)/2 (hollow cylinder), and Lc = L (plate/slab). tant. For the YS catalyst, the maximum value of ϕ was 0.94
I DOI: 10.1021/acs.iecr.7b00053
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Industrial & Engineering Chemistry Research
Figure 6. Methane selectivity as a function of Thiele modulus (a) for
spherical particle under different conditions (shown in legend) and (b)
for different shapes and conditions (shown in legend). Base case: T =
473 K, P = 25 bar, H2/CO = 2, XCO = 0%. Other conditions: Legend
shows numerical value of condition that was changed from its base case
value, whereas the remaining conditions are kept at the corresponding
base case values.
(corresponding to dp = 4 mm) for the range of conditions
investigated because of low activity of this catalyst compared to
the CAER catalyst. Most of the points for the YS catalyst are in
the region of negligible diffusional resistance (ϕ < 0.46). In the
region 0.8 < ϕ < 1, the effectiveness factor for the YS catalyst is
higher than that for CAER catalyst (spherical geometry, H2/CO
= 2).
Our results are in qualitative agreement with previous studies
on the effect of catalyst shape on the effectiveness factor as a
function of generalized Thiele modulus. Rester and Aris67
reported that maximum deviation between flat plate and
spherical particle for a first-order reaction is 14−16% and occurs
for 1.3 < ϕ < 1.7. Knudsen et al.68 showed that deviations could
be higher (up to 27.2%) for some forms of LH kinetics in the
region of ϕ values between 1 and 1.5.
Figure 5b shows data for CAER catalyst and spherical particle
(P = 20−30 bar, T = 473−493 K, H2/CO = 2, XCO = 0−50%). As
can be seen, the data scatter is much less, in comparison to Figure
5a, when the effects of particle shape and catalyst type are
removed. Minor scatter is caused by differences in pressure,
temperature, and/or conversion level. The maximum value of η is
1.15 for ϕ = 0.71 (dp = 0.4 mm at 493 K, 30 bar and XCO = 0%),
whereas the maximum value of η at base case conditions (473 K,
25 bar, XCO = 0%) is 1.12 at ϕ = 0.77 (dp = 0.6 mm).
Methane selectivity as a function of generalized Thiele
modulus is shown in Figure 6a (spherical particle) and Figure
J DOI: 10.1021/acs.iecr.7b00053
Article
6b (slab, eggshell, and hollow cylinder). Methane selectivity does
not depend only on ϕ, but also on temperature, H2/CO ratio
outside the particle, and conversion level in the reactor (i.e., on
partial pressure of water at the catalyst surface); therefore, data
were grouped into several categories. Legends in Figure 6 show
which condition was changed relative to base case value, while
the remaining conditions are kept at the corresponding base case
values. For ϕ < 0.7, average methane selectivity is nearly constant
and then starts increasing rapidly with increasing value of the
Thiele modulus (Figure 6a). Decrease in the H2/CO ratio results
in lower CH4 selectivity compared to the base case (H2/CO = 2),
but the impact is small in the kinetically controlled region (ϕ <
0.6−0.7), whereas the effect is much more pronounced as ϕ
increases. Increase in CO conversion results in significant
reduction of CH4 selectivity (XCO = 50% vs XCO = 0%) even in
the kinetically controlled region. As stated earlier, this is caused
by higher partial pressure of water which inhibits methane
formation rate (see eq 7). Increase in temperature to 493 K leads
to increase in CH4 selectivity for all values of ϕ. At both
temperatures, CH4 selectivity starts increasing rapidly for ϕ > 0.7.
Changes in pressure (20 or 30 bar) have small effect in both
kinetic (ϕ = 0.48−0.56) and diffusion control (ϕ = 2.4−2.8)
regions.
Selected CH4 selectivity data for different shapes (slab and
hollow cylinder) and eggshell distribution with spherical particle
with dp = 2 mm are shown in Figure 6b for ϕ values less than 1.3.
The qualitative trends regarding the influence of H2/CO ratio,
CO conversion, temperature, and pressure are the same as in the
case of spherical particles with uniform catalyst distribution. In
this case, the kinetically controlled region extends to ϕ ≈ 0.9.
Both higher CO conversion and lower H2/CO feed ratio have
beneficial effect on CH4 selectivity, and the combined effect (H2/
CO = 1.7 and XCO = 50%) results in significant reduction in CH4
selectivity relative to the base case conditions.
From data shown in Figure 6 we can estimate the maximum
particle size (sphere) or thickness of catalyst layer for slab and
eggshell catalyst distribution for which the intraparticle diffusion
limitations may be considered to have negligible effect on CH4
selectivity at base case conditions for the CAER catalyst. We
define negligible effect on CH4 selectivity as a value of ϕ where
the increase in CH4 selectivity is less than 6% of the value
corresponding to minimum CH4 selectivity at the base case
conditions and beyond which CH4 selectivity increases more
rapidly. The minimum value of CH4 selectivity for CAER catalyst
at the base conditions for all shapes considered is 5.60%. Using
the maximum 6% increase in CH4 selectivity as the criterion, this
gives the following values for the magnitude of ϕ: 0.65 for
spherical particle with uniform catalyst distribution and 0.90 for
all others (slab, hollow cylinder, and eggshell distribution). In
terms of particle size or catalyst layer thickness, we obtain dp =
0.50 mm for a spherical particle with uniform catalyst
distribution; L = 0.116 mm (slab/flat plate thickness); δ =
0.132 mm (eggshell thickness in 2 mm spherical particle); and ro
− ri = 0.232 mm (hollow cylinder with the outer radius of 1 mm).
It should be noted that in all these cases the catalyst effectiveness
factor is greater than 1 (η = 1.08−1.12).
4. CONCLUSIONS
We have utilized a simple one-dimensional catalyst particle
model which consists of four second-order differential equations
for reactants (H2 and CO) and product species (H2O and
C6H14) and an algebraic equation for methane formation rate in
terms of concentrations of H2, CO, and H2O inside the particle.
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Industrial & Engineering Chemistry Research
Numerical solution of this model enables one to calculate two
key performance parameters: catalyst effectiveness factor and
methane selectivity (both local and average). Kinetic parameters
for the rate of CO consumption and rate of CH4 formation were
determined from experimental data with a state-of-the art 25%
Co/0.48% Re/γ-Al2O3 catalyst (CAER catalyst).
It was shown that activity of CAER catalyst is 15−37 higher
(depending on process conditions) than that of Yates and
Satterfield catalyst. Kinetic parameters for YS catalyst were used
in several recent modeling studies of diffusion with chemical
reaction. The use of kinetic parameters derived from original
experimental data with YS catalyst severely underestimates the
importance of diffusional limitations in FTS under conditions
representative of industrial practice. From numerical simulations
with kinetic parameters for CAER catalyst, the following
conclusions can be made:
• The use of small spherical particles (0.2−0.5 mm) or
eggshell distribution with a larger spherical particle (dp = 2
mm) with catalyst layer thickness less than approximately
0.13 mm is needed to avoid negative impact of diffusional
limitations on CH4 selectivity. The catalyst effectiveness
factor under these conditions is slightly higher than 1
because of negative reaction order with respect to CO at
high CO concentrations (i.e., low CO conversion inside
the particle).
• For monolith reactors with wash-coated catalyst, diffu-
sional limitations can be avoided by using catalyst layer
thickness less than 0.12 mm at base case conditions (473
K, 25 bar, H2/CO = 2, XCO = 0%).
• Methane selectivity decreases with increase in overall CO
conversion along the reactor because of presence of water
which inhibits CH4 formation rate.
• The use of substoichiometric H2/CO feed ratios (H2/CO
= 1.7 and 1.4 in our study) leads to improvement in lower
values of CH4 selectivity (lower H2/CO ratio inside the
pellet). This is consistent with results reported by Vervloet
et al.7
• Total pressure (20−30 bar) has a small effect on the
catalyst effectiveness factor and CH4 selectivity.
• Temperature (473−493 K) has a small effect on the
effectiveness factor, but CH4 selectivity increases signifi-
cantly with increase in temperature.
• Graphs of η versus ϕ presented in the paper can provide
rough estimates of η for other Co-based FT catalysts
provided that sufficient information is available to calculate
the value of ϕ. The biggest errors would occur in the
region 0.5 < ϕ < 1.5.
To capitalize on some of these findings in practical
applications, one would need to develop preparation methods
which increase catalyst loading in a layer near the surface
(eggshell catalyst distribution) and develop Co catalysts that are
stable during long-term operation at low H2/CO feed ratios.
■
AUTHOR INFORMATION
Corresponding Author
*Chemical Engineering Program, Texas A&M University at
Qatar 219S Texas A&M Engineering Building, Education City,
PO Box 23874, Doha, Qatar. Tel.: +974 4423 0134. Fax: +30
2310 996184. E-mail: dragomir.bukur@qatar.tamu.edu.
ORCID
Dragomir B. Bukur: 0000-0002-5065-4163
K DOI: 10.1021/acs.iecr.7b00053
Article
Notes
The authors declare no competing financial interest.
∥
Deceased.
■
ACKNOWLEDGMENTS
This research was made possible by a grant (NPRP Grant 7-559-
2-211) from the Qatar National Research Fund (a member of
Qatar Foundation). The statements made herein are solely the
responsibility of the authors.
■
NOTATION
a = adsorption coefficient for CO reaction rate (bar−1)
aM = reaction order of CO in methane formation reaction
AM = pre-exponential factor for CH4 reaction rate coefficient
(mol kg−1 s−1 bar−0.29)
bM = reaction order of H2 in methane formation reaction
Ci = concentration of species i in liquid phase (mol m−3)
CL = total liquid phase concentration (mol m−3)
dp = sphere particle diameter (mm)
De,i = effective diffusivity coefficient of species i in particle
(m2 s−1)
Dwax,i = diffusivity coefficient of component i in wax (m2 s−1)
EM = activation energy for CH4 reaction (J mol−1)
Hi = Henry’s law constant for component i (bar)
k = reaction rate coefficient for CO consumption reaction rate
(mol kg−1 s−1 bar−2)
kM = CH4 formation reaction rate constant (mol kg−1 s−1
bar−0.29)
keff = effective thermal conductivity of catalyst particle
(W m−1 K−1)
L = slab thickness (mm)
Lc = characteristic diffusion length (mm)
Lg = geometric characteristic length (mm)
mM = water effect coefficient in CH4 formation equation
P = total pressure (bar)
Pi = partial pressure of component i (bar)
r = variable radius within sphere and hollow cylinder (mm)
ri = hollow cylinder inner radius (mm)
ro = hollow cylinder outer radius (mm)
R = sphere radius (mm)
RCH4 = reaction rate of CH4 (mol kg−1 s−1)
RCO = reaction rate of CO (mol kg−1 s−1)
R̅ CO = dimensionless CO reaction rate
Rg = universal gas constant (J mol−1 K−1)
S = surface area of catalyst exposed to surrounding fluid (m2)
SCH4 = local methane selectivity (%)
SC̅ H4 = average methane selectivity (%)
T = temperature (K)
V = volume of catalyst loaded region (m3)
x = dimensionless length
XCO = CO conversion (%)
yi = dimensionless concentration of species i in liquid phase
z = variable length within slab (mm)
Greek Letters
α = chain growth parameter
δ = eggshell layer thickness (mm)
ε = pellet porosity
η = effectiveness factor
νi = stoichiometric coefficient of species i
ρp = catalyst density (kg m−3)
ρw = wax density (kg m−3)
τ = pellet tortuosity
Ind. Eng. Chem. Res. XXXX, XXX, XXX−XXX
Industrial & Engineering Chemistry Research
ϕ′i = dimensionless Thiele modulus based on geometric
characteristic length of a particle
ϕ = generalized Thiele modulus based on characteristic length
for diffusion
Superscripts
s = value at the surface
■
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M DOI: 10.1021/acs.iecr.7b00053
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