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Development of a Kinetic Model for Supercritical Fluids


Fischer-Tropsch Synthesis
Aswani K. Mogalicherla and Nimir O. Elbashir*
Chemical Engineering Program, Texas A&M University at Qatar, PO Box 23874, Doha, Qatar
ABSTRACT: Kinetic models for Fischer-Tropsch synthesis (FTS) were derived to express the reaction behavior in either
conventional reaction media (gas-phase) or nonconventional media (near-critical and supercritical solvent media). These models
we developed from experimental data generated from a commercial alumina supported cobalt catalyst (15% Co/Al2O3) in a xed
bed reactor. Two models were developed: the rst one assumes ideal gas phase behavior for the gas phase reaction and uses partial
pressures to express reactant and product concentrations in rate expressions while the second model accounts for the nonideal
behavior of the reaction mixture under elevated pressures via the utilization of fugacity parameters and fugacity coecients. The
fugacity coecients were estimated from a modied Redlich-Kwong-Soave equation of state. A comparison was conducted
between the estimated kinetic parameters from the fugacity-based kinetic model and the partial pressure based kinetic model. The
heat of adsorption of carbon monoxide and hydrogen was calculated from the estimated kinetic parameters and an attempt was made
for qualitative analysis of mechanistic details of the reaction in both near critical and supercritical FTS and gas-phase FTS. It was
observed that the fugacity-based models more accurately predict the carbon monoxide consumption rates in the gas phase as well as
in near critical and supercritical FTS conditions. Similarly, the fugacity-based model was found to successfully predict the methane
formation rates for both gas phase FTS and the near critical and supercritical phase FTS.

1. INTRODUCTION
Fischer-Tropsch synthesis (FTS) holds great potential for
the production of ultraclean transportation fuels, chemicals, and
other hydrocarbon products through the conversion of readily
available syngas (CO/H2) from abundant resources (coal,
natural gas, and biomass). The conventional FTS reactors have
dierent inherent limitations depending on the type of reactor
and its congurations; such as controlling reaction selectivities,
pore diusional resistance, hot spots formation, catalyst deactivation, catalyst separation, etc. Conducting FTS reactions in
supercritical uid (SCF) media has been demonstrated to have
certain advantages over the traditional routes.1-12 The advantages can be attributed to the use of SCF solvents which oer
high diusivities (relative to a liquid), high solubilities, and
improved heat transfer properties (relative to a gas). It was
claimed that the enhancement in the production of heavy
hydrocarbons in the supercritical phase FTS relative to the
conventional media is a direct eect of the increased solubility
of hydrocarbons in the supercritical solvent media that also
enhance the in situ extraction of products and secondary
reactions.13,14
The most common commercial FTS catalysts are either ironbased or cobalt-based catalysts, while other catalysts like ruthenium and nickel have also been considered but only in lab scale
reactors. The industry is currently focusing on cobalt catalysts
due to their high FTS activity, better catalyst stability in hydrogen
rich environments, and lower selectivity to oxygenated
compounds.15,16 The FTS reaction is a surface-catalyzed polymerization process, whereby adsorbed CO and H2 molecules react
on the surface of a catalyst with adsorbed hydrogen to form
monomers (e.g., CHx based on the widely accepted surface
reaction model) that further react to give a wide spectrum of
carbon products (C1-C60). Several extensive studies reported
r 2011 American Chemical Society

attempts to understand and model the kinetics of the FTS


reaction over a number of cobalt-based catalysts. Nevertheless,
most of these kinetic models have not covered high pressure
operation as the one required for the supercritical solvent FTS
operation.17-19 Under such high pressure operation, classical
chain-growth models, such as the standard Anderson Schultz
Flory (ASF) model, cannot satisfactorily predict the product
distribution of FTS reaction. Similarly, high pressure operation
signicantly inuences the activation and deactivation of FTS
catalytic systems.20 Few reports addressed the development of
kinetic models for the FTS reaction under near critical and
supercritical conditions. The power law models were developed
by Bochniak and Subramaniam4 and Fan et al.21 to predict the
reaction kinetics in near-critical and supercritical FTS conditions
over an iron-based catalyst. In their studies, the major objective
was to estimate the catalyst eectiveness factor in supercritical
conditions and to compare it to conventional gas phase reaction
under equivalent conditions. Elbashir and Roberts10 reported a
mechanistic model using the Langmuir-Hinshelwood-HougenWatson approach for a cobalt based catalyst. Irankhah et al.22
extended this model to a Co-Ru/Al2O3 catalyst tested under
supercritical conditions. These mechanistic models were developed assuming ideal gas-law behavior and were found to be in
reasonable agreement with the experimental data obtained
from the conventional gas-phase FTS operation; however, they
failed to predict the reaction kinetics under near critical and
supercritical operations.10 Despite the agreement on the nonideality of FTS reaction behavior in near critical and supercritical conditions phase relative to conventional reaction
Received: October 3, 2010
Revised:
January 22, 2011
Published: March 01, 2011
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hexane to syngas ratios and H2/CO ratios has also been


considered. A total of 14 experimental points were used in
estimating parameters for SCF-FTS kinetics, and 9 data points
were used in estimating parameters for gas phase FTS kinetics.
The product distribution obtained at typical operating conditions of supercritical phase FTS and gas phase FTS is shown in
Figure 1. In order for us to simplify the prediction of the kinetic
parameters under such nonideal reaction conditions, we developed an approach outlined in Figure 2 that provides a simultaneous assessment of the inuence of the reaction conditions
(temperature, pressure, solvent/syngas ratio, etc.) on the reaction kinetics as well as on the phase behavior and the thermophysical characteristics of the reaction mixture. At the rst stage
of the model development, the thermodynamic analysis to
account for the phase behavior of the SCF-FTS reaction mixture
was carried out separately from the kinetic model. However,
during the parameter estimation stages the two models were
integrated.
2.1. Rate Equations and Mathematical Expression for
Reactor Models. Subramaniam and McHugh23 reported that
in supercritical conditions, pressure effects on rate constants are
dominant only for pressures more than 99 bar and solute
(reactants and products) mole fractions in reaction media less
than 0.15. In the present work, the maximum operating pressure
is 80 bar and the solute mole fraction (syngas mole fraction) is
around 0.25. Elbashir et al.11 have conducted experiments by
keeping the partial pressure of syngas constant and varying the
system pressure using Argon to maintain constant space velocity.
The difference between the two experiments was too small, and it
conforms that there was no pressure effect on the observed
reaction kinetics in gas phase FTS. In supercritical conditions, the
pseudo first-order rate constant obtained from experimental
rates (observed rate of reaction/operating pressure) was invariant with the density of the supercritical solvent, indicating that
kinetic constants reported in the present analysis are free of
pressure effects.24 Thus, the pressure effects on rate constants
were neglected and only the effect of thermodynamic nonidealities on reaction rates were considered in the proposed kinetic
model. One of the most common assumptions of the kinetic
models for the FTS reaction over cobalt based catalysts is to
consider the hydrogenation of surface carbon as the rate-determining step. Similar assumptions have been used in developing
kinetic models for the reaction in near critical and supercritical
conditions, expressing reaction rates in terms of partial
pressures.10 Even though the high pressure supercritical reaction
media is likely to result in thermodynamic nonidealities, most of
the previous kinetic models for near critical and supercritical FTS
models have utilized the partial pressure of reactants in their rate
expressions.23 Elbashir and Roberts10 suggested using activities
rather than partial pressures to more accurately predict kinetics
under supercritical conditions. In the case of insignificant pressure effects on reaction rate constants, the rate expression derived
for gas-phase reactions can directly be extended to supercritical
conditions simply by replacing the partial pressure of reactants
and products with fugacities. This approach was adopted by
Ermakova et al.25 in kinetic modeling of supercritical FTS
reaction on an iron-based catalyst.
The model adopted in the present study is based on previous
kinetic models for cobalt-based FTS catalysts.10,17,26 The rate
expressions are derived utilizing the Langmuir-HinshelwoodHougen-Watson (LHHW) approach. Considering our experimental data that show very low selectivity toward CO2, the rate of

Figure 1. Product distribution at 523 K for dierent pressures in SCFFTS and gas phase FTS.

media, there is still a need for quantitative assessment of the


kinetic model under such conditions. The objective of the
present study is to investigate the possibility of accounting for
the nonideality of this reaction in supercritical phase via
extending the widely accepted kinetic model for cobalt catalysts
in gas-phase FTS to supercritical FTS by accurately representing reactant concentrations. The developed kinetic models for
the FTS reaction in this study have been represented in terms of
fugacity parameters and fugacity coecients, and they show
good credibility in predicting the reaction behavior over a wide
range of operating conditions.

2. KINETIC MODELING
In the present work, a kinetic model was derived based on
experimental data obtained from a commercial cobalt catalyst
(15 wt % Co/Al2O3) where testing was conducted in gas phase,
near-critical, and supercritical media composed of hexanes in a
xed-bed reactor. The experimental data on which this model is
based were reported in the work of Elbashir and Roberts11 and
Elbashir et al.12 The reactor was allowed to run continuously
until steady state performance was achieved, with respect to
conversion and selectivity, as determined by product analysis
from the GC data. For the gas phase FTS, the steady state
performance has been achieved after approximately 24 h timeon-stream (TOS), while for the supercritical hexanes FTS it
requires around 48 h TOS to reach steady state performance.
The average carbon number calculated from experimentally
determined hydrocarbon product distribution was in the range
of 9.5-11 for SCF-FTS and 5.0-6.6 for gas phase FTS.
According to their report,12 the optimal reactor performance
for FTS reaction under near critical and supercritical solvent
conditions (will later be referred to as SCF-FTS) was obtained
for an H2/CO ratio (V) of 2 and hexanes (solvent)/syngas ratio
(S) of 3/1. The following experimental conditions have been
selected to develop these kinetic models: temperature range
230-250 C (503-523 K), pressure range 35-79 bar, H2/CO
feed ratio of 2-1, with supercritical solvent (hexanes)/syngas
molar ratio of 3/1 (i.e., S = 3), and CO ow rate varied from
8.1  10-4 to 16.2  10-4 mol/s. For the gas phase reaction, the
partial pressure of syngas was kept constant and argon was used
as inert media to maintain the desired space velocity. Under such
reaction conditions, carbon monoxide conversion was found to
vary between 30 and 85%, corresponding to an integral reactor
performance. Few experimental data (four data points) at other
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Figure 2. Schematic of the approach to develop a kinetic model for FTS in near critical and supercritical reaction media.

oxygen removal by water formation has been equated to the rate


of carbon hydrogenation (both are the slowest steps in the
reaction). To account for the nonideality of the FTS reaction in
the near-critical and supercritical phase operation (SCF-FTS),
the partial pressures in the reaction rate expressions as in the
work of Elbashir and Roberts10 have been replaced by the
fugacities. The temperature dierence in the catalyst particle
was estimated to be 0.34 K, and by using the Damkohler
equation, we found that the catalyst particles are isothermal,
which indicates the absence of hot spot formation.27 The
external temperature rise in the bulk reaction phase has been
determined from (T)bulk = [dP  rateobserved  (-H)]/
(6CPfGjHNPr-0.67) and was 2.3 K in supercritical phase FTS
and 5.2 K for gas-phase FTS.27 These numbers are nearly
matching with the temperature rise reported in the middle of
the reaction bed on the same experimental set up in an
independent study.28 For this range of temperature gradients,
the increase in reaction rate due to temperature rise of the bulk
gas phase will be compensated by decrease in concentration at
the catalyst surface, and as a result, we consider our assumption
of isothermal reaction to be appropriate. The presence of the
external mass transfer from the bulk gas phase to the catalyst
surface has also been veried utilizing Mears criterion for
external diusion. For all the experiments, the dimensionless
number (rateobserved  Fb  dp)/(2kC  Cbulk) was found to
be less than 0.1 indicating that the reaction is away from external
mass transfer limitations at the specied conditions. The physical properties of the uids required for above analysis were
adopted from ASPEN Plus2006 and the correlations for heat
and mass transfer were taken from standard chemical reaction
engineering textbooks.27 Finally, the following assumptions
have been made to develop this kinetic model:
(1) At any location inside the reactor cross section, the
product distribution, average carbon number, and hydrogen usage ratio are assumed to be similar to that at
the reactor outlet.
(2) The reactor is operating under isothermal conditions.
(3) Internal and external mass transfer limitations inside the
catalyst bed have been neglected under the specied
reaction conditions.

The mathematical expressions of the rate equations used in


this study are listed in Table 1. The active length of the reactor
bed was estimated to be around 2 cm based on a catalyst loading
of 1 g (screened to 100-150 m of particle size) in an HIP highpressure reactor bed of a conventional downow xed-bed
stainless steel reactor (1.27 cm  25.4 cm; eective volume:
32 cm3). The bed porosity was calculated from the available
correlations to be around 0.32 based on catalyst particle size and
reactor diameter, assuming that the catalyst particles have
irregular shapes.
2.2. Estimation of the Fugacity of Carbon Monoxide
and Hydrogen under Typical Fischer-Tropsch Synthesis
Operation. In the present study, the fugacity of the FTS reaction
mixture has been evaluated using the modified Soave-RedlichKwong EOS and the mixing rules proposed by Yermakova and
Anikeev.29 The primary reason for choosing the SRK EOS in this
analysis is the ability of SRK EOS in predicting the phase
behavior of FTS reaction mixture which has been well-demonstrated in the literature.25,29,30 Water is one of the major FTS
products; the amount of water present in the reaction mixture is
relatively small compared to amounts of hydrocarbon solvent
present in the system. The advantages of the Peng-Robinson
EOS over SRK EOS have been demonstrated only for CO2- or
water-rich supercritical reaction systems.31,32 However in near
critical and supercritical FTS, the reaction mixture is rich in
hydrocarbon solvent(hexane) where the SRK EOS accurately
represents phase behavior. The fugacity parameters and fugacity
coefficients for this model represent all components in the FTS
reaction mixture including reactants (CO and H2) and typical
products (olefins (C2-C22), paraffins (C1-C25), water) in
addition to the solvent in SCF-FTS that has been represented
by hexanes (C6 mixture). Figure 3 shows the outline and the
equations used to estimate the fugacities of the aforementioned
compounds.29 The constants Kij and Cij in the above procedure
are binary interaction parameters, which are normally estimated
from thermodynamic experimental data. In general, these interaction parameter values are too small having an order of
magnitude 10-2 and are considered as zero in the vapor-liquid
equilibrium (VLE) estimation, except in few cases such as for the
hydrogen-hydrocarbon mixtures. Nevertheless, in the present
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Table 1. Rate Equations, Fugacity Coecients, and Reactor Model Equationsa


CO consumption rate (mol/gcat 3 min)

rCO

CH4 formation rate (mol/gcat 3 min)

rCH4

fugacity coecient () and fugacity of CO and H2

H2
fCO

KfCO 1=2 fH2 1=2


1 K1 fH2 1=2 K2 fCO 1=2 K3 fCO 2
1 fH2
2 1 3 fCO 1=2 fH2

- 1=2 1=2

- 1 - 1 1

fH2
YH2 P;

fCO
YCO P

1 - XCO
DNMNA

CO

V-

PCO ;

fH2

2N M
XCO
2N
DNMNA


PH2

where
DNMNA : 1 V S SV - 2N M=2NX CO X CO =N

where DNMA refers to the denominator of the fugacity term of CO


rCO Fcat 1 - b Acr
dXCO

dH
FCO
dXCH4
rCH4 Fcat 1 - b Acr

dH
FCO

isothermal plug ow reactor models for CO conversion and CH4 yield

Where V is H2 to CO feed ratio; S is the hexane to syngas feed ratio; XCO is conversion of carbon monoxide at any catalyst bed cross section; XCH4 is
methane yield; H is the catalyst bed height; FCO
is inlet molar ow rate (mol/min) of CO; Acr is the reactor cross section; b is the bed porosity; Fcat is the
catalyst particle density; P is the total pressure; i is the fugacity coecient; Yi is the mole fraction of the ith compound in the reaction mixture; k, K1, K2,
K3, 1, 2, 3 are the kinetic parameters; at H = 0, XCO = 0 and XCH4 = 0.

MATLAB, uses genetic algorithm). This objective function was


defined as (all_points_i(Xexpt,i - Xmodel,i)2) where Xexp represents
the experimentally determined CO conversion or CH4 selectivity
and Xmodel represents the corresponding values determined by
the model. A similar optimization technique was applied to
estimate the kinetic parameters for CO conversion rates and
CH4 formation rates. In the earlier studies on the same kinetic
model, the temperature sensitivity of kinetic parameters was not
accounted and they were assumed as constants.10,22 As outlined
in Figure 2, the parameter estimation was conducted for reaction
conditions at two temperatures 513 and 523 K and at specified
reaction conditions (e.g., pressure, hexane (SCF) to syngas ratio
(S), H2/CO ratio (V), and CO flow rate). The physical
significance and the temperature sensitivity of the estimated
parameters were examined. It has been widely accepted that the
kinetic parameters are sensitive to the reaction temperature and
follow the Arrhenius law in temperature dependence. As described in Figure 2, parameter estimation has been conducted at
two levels. At the initial level, parameters were estimated for each
temperature. At that stage, the total number of parameters
estimated was four in CO conversion kinetics and the total
number of parameters in CH4 yield models was three. In the next
level, Arrhenius law was incorporated into the parameters to
evaluate the temperature sensitivity model. The pre-exponential
factor and activation energy for each kinetic parameter was
evaluated in the second level. Therefore, the number of parameters estimated in the second level of the CO conversion model
is eight (4  2). Similarly, the total number of parameters in the
methane yield model is six (3  2). The nonlinearity of the rate
expression drastically increased after incorporating Arrhenius
expressions in the reaction rates equation. As a result, the
parameter estimation process becomes less accurate and more
difficult due to the strong correlation between the pre-exponential factor and activation energy. Froment33 suggested incorporating the reparameterization at mean temperatures in kinetic
modeling to resolve this issue. In the present case, 513 K was
considered as the average temperature to estimate the parameters for the CO consumption rate while 523 K has been

Figure 3. Equations used for fugacity estimation.

work binary interaction parameters were set to zero due to a lack


of experimental VLE data under the specified reaction
conditions.
2.3. Parameter Estimation. The equation for CO conversion
was integrated with respect to reactor length using an ordinary
differential equation solver in MATLAB (ODE45). The fugacity
coefficients were determined in terms of CO conversion, hexane/syngas ratio, H2/CO ratio, temperature, and pressure separately and then incorporated to be part of ODE45. The kinetic
parameters were optimized by least-squares regression analysis.
The Maltlab function called lsqnonlin which uses the Levenberg-Marquardt algorithm was used for the optimization of the
objective function. For getting an initial guess of the parameters
during isothermal parameter estimation, an objective function
(showed below) was minimized using the genetic algorithm
function in MATLAB (minimization and fitness function of
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Figure 4. Partial pressures vs fugacity along the reactor length at 523 K and 79 bar (a) for carbon monoxide and (b) hydrogen.

3. RESULTS AND DISCUSSIONS

chosen for the CH4 formation rate expression, i.e.


KT

K @513 =K @513 K T K @513 exp- E=R1=T- 1=513

3.1. Fugacity of H2 and CO. As shown in Figure 3, there are


three roots for the compressibility factor Z while solving the
fugacity using the modified RKS EOS. A similar approach has
been adopted by Masuku et al.34 for estimating the chain growth
probability in FTS. In reality, phase splitting or condensation
inside catalyst pores takes place whenever a sufficient amount of
long chain hydrocarbons are present. The reaction conditions
used for this study are supposed to yield a single phase for the
SCF-FTS according experimental measurements of the phase
behavior and the visualization of the critical properties for a
typical reaction mixture in a variable-volume-view-cell in previous

13
K iT K i@513 =K i@513 K iT K i@513 exp - H i =R1=T - 1=513

14

similarly iT i@513 exp - ei =R1=T - 1=523 and i 1 - 3

15

where E is the activation energy of FTS, Hi is the heat of


adsorption, and ei the activation energy for parameters in the
methane yield model.
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Table 2. Isothermal Parameter Estimation for near Critical


and Supercritical Conditions
K  104 (mol/
temperature, K
523
513

K1  102

K2  102

0.5

K3  104

0.5

gcat 3 min 3 bar)

(1/bar )

(1/bar )

(1/bar)

6 ( 0.5
3.5 ( 0.65

12 ( 2
17 ( 3

50 ( 4
27 ( 3

1 ( 0.3
2 ( 0.8

Table 3. Final Estimates of the Kinetic Parameters for


Supercritical FTS
fugacity based

partial pressure

model

based model

parameter
K@513 (mol/gcat 3 min 3 bar)
0.5

Figure 5. Partial pressure vs fugacity coecient along the reactor length


at 523 K and 79 bar for carbon monoxide and hydrogen.

K1@513 (1/bar )
0.5

K2@513 (1/bar )
K3@513 (1/bar)

reports.11 On the other hand, our findings showed a maximum


chain growth probability of 0.70 for the gas-phase FTS and 0.85 for
the SCF-FTS (which is in agreement with the data of Biquiza
et al.35). In a typical integral reactor both the conversion and the
chain growth probability increase axially from the inlet to the outlet
of the reactor bed resulting in a great possibility of single phase
operation over a large fraction of the reaction bed. As a result, we
simplified our calculations by assuming a single phase for the
reaction mixture under the specified conditions. Thus, the largest
real root for Z has been selected. It was observed that Z is sensitive
to CO conversion as well as to the hydrocarbon product distribution from the synthesis reaction. The calculated values of Z were
found to vary from 0.9 to 1.7 as a function of the reaction conditions.
Our ndings show that under typical SCF-FTS operating
conditions (e.g., 250 C and 79 bar for hexane/syngas ratio of
3 and H2/CO feed ratio of 2), the partial pressure of CO and H2
dropped from 6.6 to 1.1 bar and 13.2 to 1.8 bar, respectively. The
fugacity estimated in the present work is not only sensitive to
reactants concentrations but also to the product distribution.
The variation of partial pressure and fugacity along the reactor
length is shown in Figure 4. It can be observed from Figure 4 that
there is a dierence between the partial pressure of carbon
monoxide and hydrogen and the respective calculated fugacity
parameters. The variation of fugacity coecients with reactant
partial pressures in the reactor is shown in Figure 5. As shown in
Figure 4, the dierence between the partial pressure and the
calculated fugacity parameters is more signicant at the reactor
inlet (high CO and H2 partial pressures); however, Figure 5
shows lower fugacity coecients at the reactor outlet (low CO
and H2 concentrations). The decrease in the fugacity coecient
indicates an increase in the nonideal behavior of the FTS reaction
mixture as CO and H2 conversion increases. These ndings also
show that the products forming during the FTS reaction have
great impact on the concentration of reactants on the catalyst
surface. For a similar process, Zimmerman and Bukur36 lumped
the whole product distribution prole into propylene and
calculated the fugacity coecients as 1 ( 0.05. A similar attempt
was made in this study to investigate the eect of lumping
hydrocarbon products from FTS into single compound (e.g., C5
paran). In that case, a marginal decrease in fugacity coecient
was observed. As a result, a typical hydrocarbon product distribution was used to estimate the fugacities and the fugacity
coecients in the supercritical FTS media. The sensitivity
analysis of estimated fugacities has been conducted by using

-4

(3.5 ( 0.7)  10-4

(4 ( 0.5)  10

(16.9 ( 1.1)  10

-2

(15.0 ( 1.6)  10-2

(20.0 ( 1.2)  10

-2

(17.1 ( 1.1)  10-2

-4

(2 ( 0.4)  10

(1.5 ( 0.2)  10-4

E (kJ/mol)

103.9 ( 2.6

91 ( 4.4

H1 (kJ/mol)

-50.1 ( 3

-74 ( 11.1

H2 (kJ/mol)
H3 (kJ/mol)

149.5 ( 5.5
-99.7 ( 11.1

151 ( 7.1
-107 ( 6.2

R2 (SSreg)

0.92

0.80

binary interaction parameters reported by Biquiza et al.35 where


the interaction parameters for CO, H2, and hexane with hydrocarbon compounds were expressed in terms of carbon number.
As shown in Figure 5, the fugacities of CO and H2 were
marginally inuenced with the binary interaction parameters.
Therefore, further studies were conducted without binary interaction parameters.
3.2. Parameter Estimation for Rate of CO Consumption.
Even though the kinetic model used in the present study has been
widely accepted in literature, the temperature sensitivity of the
kinetic parameters has not been taken into consideration.17,22 To
investigate the significance of temperature sensitivity, our model
parameter estimation was conducted at two different temperatures (513, 523 K). These temperatures have been selected based
on the previous assessment of the optimum operating conditions
for the SCF-FTS.11,12 The estimated kinetic parameters of the
isothermal conditions are shown in Table 2 for two temperatures
under typical experimental conditions within the near critical and
supercritical region .11
As shown in Table 2, the model parameters are sensitive to
temperature, since the kinetic constant K increases with temperature while the adsorption constants K1 and K3 decrease with
temperature. Nevertheless, the term K2 was found to increase
with the temperature. K2 is a function of the rate constants of
OH* radical formation (kO1) and CH* radical formation (kC1).10
The parameter K2 can also expressed as follows17,10
K2 KC

p
p
kcf 1= kcf

where KC is the dissociative adsorption equilibrium constant for


CO and kcf is (kO1/kC1).
The parameter K2 is sensitive to the temperature and it
depends on the heat of dissociative adsorption of CO and
activation energies of the reactions that form OH* and CH*.
For nonisothermal conditions, the initial guess values for activation energy for the parameters were calculated from parameters
estimated at 513 and 523 K.
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Figure 6. Comparison between experimental values of CO conversions and the estimated values by the fugacity based model and the partial pressure
based model in SCF-FTS as function of (a) temperature at P = 65 bar, S = 3, and V = 2 and (b) pressure at T = 523 K, S = 3, and V = 2.

A similar approach was applied in the estimation of the kinetic


parameters using the reactants partial pressures instead of
fugacities in developing the kinetic model. The nal estimates
for the values of the parameters for both fugacity based and
partial pressure based kinetic models and parameter 95% condence intervals are shown in Table 3. All condence limit values
are much smaller than the parameter mean values indicating that
regression analysis is meaningful. The estimated CO conversions
and experimentally determined CO conversion at dierent
pressures and temperatures are plotted together in Figure 6.
Under testing conditions in SCF-FTS, our ndings show that the
fugacity-based kinetic model has better represented the reaction
performance. A common approach to check the sensitivity of the
determined parameters is to conduct an F-test to discriminate the
kinetic model. In the present work, the F-test was conducted on
both the fugacity-based model and partial pressure-based model
and both passed that test. The F-value of the fugacity-based
model was found to be 1.6 while that of the partial pressure-based
model was found to be 2.9, both are less than the critical F-value
of 4.6. This nding is a positive sign indicating that the regression
is statistically meaningful.37 For given experimental conditions,
the maximum variation in these experimental conversions was
within 3% of the mean values reported; however the fugacity
model and partial pressure model dier by a minimum of 2% to a

maximum of 14% indicating that the dierence between partial


pressure model and fugacity model is not due to experimental
uncertainties. The goodness of t was also examined in terms of
the linear regression coecient R2 to compare experimental data
and model predicted values of CO conversion. The data listed in
Table 3 prove that the fugacity-based model statistically better
represents SCF-FTS with a higher R2 value and lower F-value
than the partial pressure model. We conducted a simple analysis
that a 20% change the in initial guess value showed a maximum
5% change in the estimated value for both the gas phase FTS and
SCF-FTS, which will not have much impact on the nal
comparisons made in this study.
Also, as shown in Table 3, there is an appreciated dierence
between the parameters estimated from the fugacity based model
and those from the partial pressure based model. The activation energy from the fugacity based model was found to be 103.9
kJ/mol whereas that from the partial pressure model was found
to be 91 kJ/mol. These values agree well with previously reported
values.38 The apparent activation energy calculated from experimental data collected at dierent temperatures from -R[(d
ln(rate))/(d(1/T))] was found to be 110 kJ/mol, which is nearly
matching the activation energy obtained from the fugacity-based
model. The heat of adsorption of H2 and CO over the cobalt
based catalyst was calculated from the kinetic parameters
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Table 4. Final Estimates of the Kinetic Parameters of GasPhase FTS


fugacity based

partial pressure

model

based model

parameter

-4

Table 5. Estimated Kinetic Parameters for CH4 Formation in


near Critical and Supercritical FTS and in Gas-Phase FTS
Reaction
parameter

-4

supercritical phase reaction

gas-phase reaction
0.145 ( 0.09

K@513 (mol/gcat 3 min 3 bar)


K1@513 (1/bar0.5)

(3 ( 1.1)  10
(24 ( 3.1)  10-2

(2.9 ( 1.2)  10
(23.3 ( 2.6)  10-2

1@523

0.105 ( 0.06

2@523

139.86 ( 11.1

96.5 ( 16.2

K2@513 (1/bar0.5)

(16 ( 2.1)  10-2

(16.5 ( 2.6)  10-2

3@523

0.073 ( 0.012

0.048 ( 0.021

K3@513 (1/bar)

(1 ( 0.25)  10-4

(1.1 ( 0.1)  10-4

e1 (kJ/mol)

16.27 ( 2.1

10.3 ( 1.1

E (kJ/mol)

74.5 ( 11.1

81 ( 5.6

H1 (kJ/mol)

-58.8 ( 4.3

-52 ( 7.1

e2 (kJ/mol)
e3 (kJ/mol)

129.2 ( 12.4
-12.05 ( 1.6

110.24 ( 7.8
2.58 ( 0.87

H2 (kJ/mol)

141.4 ( 9.3

155.1 ( 5.8

R2

0.94

0.98

H3 (kJ/mol)

-74.8 ( 5.7

-80.1 ( 3.2

R2 (SSreg)

0.85

0.84

conversions and the experimentally determined values for the


gas phase FTS at 20 bar and dierent reaction temperatures are
plotted in Figure 7. Both the fugacity and partial pressure based
models predicted fairly well the gas-phase FTS reaction performance. The F-value of the fugacity based model was found to be
around 1.05 while for the partial pressure based model it was
found to be around 1.1, both being less than the critical F-value
of 3.6. The regression coecients R2 between experimental
and model predictions of CO conversions for both the fugacity
and partial pressure based models were also found to be
identical.
The parameters for gas-phase FTS kinetics dier from those
under SCF-FTS conditions. The apparent activation energy
estimated from the kinetic parameters of the gas-phase reaction
was found to be 75 kJ/mol; however, for SCF-FTS, the activation
energy was found to be around 103.9 kJ/mol. The lower
activation energy in the gas-phase reaction could be attributed
to the diusion limitations inside the catalyst pores. Uner26 and
Kellner and Bell43 mentioned that the decrease in hydrogen
adsorption equilibrium constant results in a decrease of the
methane formation rates and increase of the chain growth
probability. Our ndings show that the hydrogen adsorption
coecient (K1) value obtained from gas-phase FTS data is higher
than the value obtained from the near critical and supercritical
phase FTS data. These results could also explain the high
methane selectivity and low chain growth probability obtained
for gas-phase FTS compared to SCF-FTS. On the other hand,
the adsorption equilibrium constant and heat of adsorption of
CO in gas-phase conditions are lower than the values obtained
from near critical and supercritical reaction generated data
indicating strong CO adsorption on active sites in near critical
and supercritical conditions compared to gas-phase conditions.
As shown in Table 4, the magnitude of kinetic parameter K2@513
is less in the gas-phase reaction conditions compared to SCFFTS. As reported earlier a smaller value of K2 can be due to the
lower magnitude of either kcf or KC. The lower kcf in gas-phase
FTS can occur when the rate constants for OH* radical formation
is smaller than the rate constant for CH* radical formation. This
normally results in lower water formation rates in gas-phase FTS
compared to SCF-FTS, and it is in agreement with previous
reports in this eld.6 For the case of high KC, the dissociative
adsorption of CO is more rapid and produces more surface
carbon and the strong carbon-metal bond leads to production
of heavier hydrocarbons. Therefore, the smaller value of K2 in
gas-phase conditions can also be due to the smaller KC i.e. the
slow rate of dissociative adsorption of CO in gas-phase FTS
conditions compared to that in SCF-FTS. The aforementioned
ndings of the kinetic models are in excellent agreement with

Figure 7. Comparison of experimental and estimated CO conversions


in gas-phase FTS at P = 20 bar, S = 0, V = 2.

obtained from the fugacity based model. The heat of adsorption


of hydrogen on the cobalt catalyst is calculated as 2(-H1)
116.2kJ/mol using the basic mechanism of the reaction whereby
K1= KH. Zowtiak and Bartholomew39 have reported that the
adsorption of hydrogen on the cobalt catalyst is an activated
adsorption process whereby the extent of adsorption is a function
of the type of catalyst support and metal loading. The heat of
adsorption of hydrogen calculated in the present work agreed
with the reported values of Zowtiak and Bartholomew39 for a 10
wt % Co/Al2O3 (105 kJ/mol) and Vannice40 for the 2 wt % Co/
Al2O3 (80 KJ/mol). Other important kinetic parameters are K3 =
KCO whereby KCO is the equilibrium adsorption coecient for
carbon monoxide and H3 which represents the heat of adsorption of carbon monoxide. In the present work, H3 was
calculated as 99.7 kJ/mol. Vannice40 reported the heat of adsorption of CO on 2 wt % Co/Al2O3 to be around 185 kJ/mol. The
heat of adsorption of CO calculated from kinetic parameters
reported by Yates and Sattereld41 was found to be around
70 kJ/mol. van Der Laan and Beenackers42 reviewed the heat of
adsorption of CO and H2 on VIII metal catalysts during the FTS
reaction. They concluded that the variations in the reported values
of the heat of adsorption of CO during FTS may be attributed to
the dierence in the reaction conditions or metal loading of the
catalyst.
Similarly, the kinetic parameters for the gas phase FTS
conditions and parameter 95% condence intervals have been
estimated following the same aforementioned process as shown
in Table 4. The comparison between the estimated CO
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Figure 8. Comparing experimental and estimated CH4 yield in SCF-FTS as a function of (a) temperature at P = 65 bar, S = 3, and V = 2 and (b) pressure
at T = 523 K, S = 3, and V = 2.

the experimental data in SCF-FTS (e.g., as discussed in refs 11


and 12).
In general, our ndings suggest that the fugacity-based kinetic
model resolves conceptual hurdles in kinetic parameter estimations for nonideal conditions such as these in SCF-FTS or high
pressure gas-phase FTS. As a result, this concept has been
extended to develop a fugacity-based kinetic model for the
estimation of the kinetics parameters for the methane
formation rate.
3.3. Parameter Estimation for Methane Formation Rates.
Methane formation is the most anomalous reaction in the set of
reactions that take place during FTS. In several studies a
remarkable decrease in CH4 selectivity was found under SCFFTS conditions compared to that under gas-phase conditions
under a wide range of reaction conditions and on different
catalsysts13 (and references therein). These results have been

attributed to the improved heat transfer in the reaction zone of


SCF-FTS, resulting from the higher density facilitated by the
presence of the supercritical solvent. The parameters for the
fugacity-based model and parameter 95% confidence intervals
were evaluated from the experimental data obtained from both
gas-phase and SCF-FTS conditions as listed in Table 5. As shown
in Figures 8 and 9, the fugacity-based model predicts fairly well
the rate of CH4 formation in both SCF-FTS and gas-phase FTS.
The activation energies and kinetic parameters in gas phase FTS
were found to be different from those of the SCF-FTS. Also, the
activation energy of methane formation was found to be significantly
lower than the activation energy of carbon monoxide consumption,
which indicates that methane formation rate is much faster than the
CHX radical formation under the reaction conditions.
As shown in the Table 5, the higher activation energy for
methane formation (e1) and the lower value of kinetic constant
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and as a result, there is a great possibility for phase splitting after a


certain conversion inside the reactor bed.29 Despite the usefulness of thermodynamics simulation models, which have been
utilized in this study, there is still a need for the experimental
measurements of the SCF-FTS phase behavior for better understanding and prediction of the reaction behavior in near critical
and supercritical conditions.

4. CONCLUSION
The focus of this study is to develop a kinetic model to predict
the reaction behavior of FTS under nonideal conditions represented by elevated pressures in conventional gas-phase FTS or
coupled with the presence of a solvent in near critical and
supercritical phase FTS conditions. In a previous study,10 we
suggested considering thermodynamic nonideality to better
represent the concentration of molecules of interest at the high
pressure operating conditions as well as to include solvent eects
on individual rate constants in the critical region and particularly
for the initiation steps. At that stage, we were able to provide a
qualitative description to the enhanced behavior of the reaction
(both on activity and selectivity) in the near critical and supercritical FTS relative to the gas-phase FTS under comparable
operating conditions (described in ref 11). The ndings of the
developed fugacity based kinetic model correlate well with the
previously proposed reaction pathway that assumes an increased
availability of active sites in the supercritical medium that
promote both the adsorption of the reactant molecules (CO
and H2) and possible incorporation of primary products (e.g., Rolens) into the chain growth process.11 In other words, operating the FTS reaction in the near critical and supercritical FTS
conditions provides more active sites on the catalyst surface with
higher coverage of active carbon than the regular ones; these sites
were assumed to suppress methane formation.
Our rst attempt to account for the nonideality of FTS
reaction at high pressure gas-phase operation and in near critical
and supercritical conditions started with the development of a
fugacity based kinetic model. The calculated kinetic parameters
for this model and its ability to predict the reaction behavior in
the near critical and supercritical FTS have been compared to
those obtained from conventional partial pressure based kinetic
model. Activation energies for a few elementary steps and heat of
adsorption for hydrogen and carbon monoxide were calculated
from the estimated kinetic parameters. Our ndings showed that
the fugacity-based models more accurately predict CO consumption rates under a variety of conditions compared to the predictions from the gas-phase FTS. On the other hand, the calculated
values of the hydrogen surface coverage, CHx monomer termination rate, and methane formation rates in the gas-phase FTS
were found to be higher than those obtained in SCF-FTS under
equivalent reaction conditions. The fugacity-based model also
allows us to calculate the fraction of vacant sites and the rate of
CO dissociative adsorption in both cases and showed higher
values in SCF-FTS. Unlike the partial pressure model,10 the
fugacity based model also successfully predicts methane formation rates in both gas-phase and near critical and SCF-FTS in a
variety of reaction conditions. Currently, the fugacity based
kinetic model is being extended to predict the hydrocarbon product distribution in the nonideal reaction mixture of
SCF-FTS.44

Figure 9. Comparison of experimental and estimated CH4 yield in gasphase FTS at P = 20 bar, S = 0, V = 2.

1@523 for SCF-FTS indicates that the reactants need more


energy for methane formation compared to that required for the
gas-phase FTS conditions. As reported in an earlier study,10 2 is
directly proportional to 1/Kt where Kt is the rate constant for the
chain termination reaction. The high value of 2 indicates low
chain termination rate in near SCF-FTS relative to gas-phase
FTS. Therefore, the chain growth probability in the SCF-FTS is
found to be higher than that of gas-phase FTS under relatively
identical conditions.
One of the major advantages of using supercritical uids in
FTS is to enhance the in situ extraction of heavy hydrocarbons
from the catalyst pores to free the active sites as well as to provide
more vacant sites for the readsorption of primary products.13 The
fraction of vacant active sties during FTS is equivalent to
(1/[1 K1(fH2)1/2 K2(fCO)1/2 K3fCO]2) as stated in the
developed kinetic model.10 Our ndings showed that at 513 K
and 20 bar syngas partial pressure, the fraction of vacant sites in
SCF-FTS is around 0.22; whereas for gas-phase FTS, it is around
0.19. This dierence in the number of vacant sites could also be
attributed to the nonidealities as accounted for by the fugacity
coecient as well as to the transport properties in the SCF media.
The active site occupancy by any oligmer (building block)
strongly depends on the concentration of the respective compounds at the active metal surface at the micro level. The
supercritical uid reduces the concentration of heavy hydrocarbon at micro levels due to its superior extraction capability. It
increases the desorption rate of heavy compounds from the
active site which is a molecular level phenomena. The primary
hydrocarbons desorbed from the active site can either readsorb
on the same active site or another vacant site (such a scenario has
been assumed in several kinetics model to describe nonideal ASF
product distribution).13 Our qualitative conclusion is that primary products have more chances to readsorb in SCF-FTS
compared to gas phase FTS.11 It has to be mentioned here that
the advantages of SCF-FTS arise from several reasons such as
improved heat and mass transfer. Along with them, having more
vacant sites is also another favored condition for obtaining
heavier hydrocarbons in SCF-FTS.
In the present work, both the partial pressure based kinetic
model and the fugacity based kinetic model assume that the FTS
reaction mixture exists as a single phase in the reactor; however,
in actual conditions the reaction mixture exists as vapor/liquid,
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AUTHOR INFORMATION

H1 = heat of adsorption (kJ/mol)


H2 = heat of adsorption (kJ/mol)
H3 = heat of adsorption (kJ/mol)
Ri = mixing parameter
i = mixing parameter
i = mixing parameter
b = bed porosity
Fcat = catalyst density (g/cm3)
i = fugacity coecient for the ith compound
1 = constant in model for rate methane formation
2 = constant in model for rate methane formation
3 = constant in model for rate methane formation, (mol/
gcat 3 min 3 bar)
i = acentric factor for the ith component of the reaction
mixture

Corresponding Author

*E-mail: nelbashir@tamu.edu.

ACKNOWLEDGMENT
The authors would like to acknowledge the nancial support
of this work by Qatar National Research Funding under grant
(NPRP 08-261-2-082). The authors would also like to acknowledge the invaluable discussion with Professor Dragomir Bukur
about this study.
NOMENCLATURE
Acr = reactor cross section (cm2)
aii = mixing parameter
am = mixing parameter
bii = mixing parameter
bm = mixing parameter
CPf = specic heat capacity of uid (cal/mol 3 K)
dp = catalyst particle diameter (cm)
E = activation energy (kJ/mol)
ei = enthalpy (kJ/mol)
fCO = fugacity of CO (bar)
fH2 = fugacity of hydrogen (bar)
= CO feed rate (mol/min)
FCO
G = mass ow rate (g/cm2 3 s)
H = catalyst bed height (cm)
jH = j factor for heat transfer
K = rate constant in LHHW model for rate of CO conversion
(mol/gcat 3 min 3 bar)
K1, K2, K3 = constants in LHHW model for rate of CO
conversion (1/bar0.5, 1/bar0.5, 1/bar)
kC = external mass transfer coecient (cm/s)
KC = CO dissociative adsorption constant (1/bar)
kC1 = rate constants of CH* radical formation (1/s)
Kcf = adsorption equilibrium constant for carbon
Ki@513 = constant in LHHW model for rate of CO conversion at
513 K (1/bar0.5)
kO1 = rate constants of OH* radical formation (1/s)
Kt = rate constant for chain termination reaction (1/s)
M = average hydrogen atoms in the Fischer-Tropsch products
mi = mixing parameter
N = average carbon number
NPr = Prandtl number
P = total pressure (bar)
PCi = critical pressure of the ith component of the reaction
mixture
R = universal gas constant (J/mol)
S = hexane to syngas feed ratio
T = reactor temperature (K)
TCi = critical temperature of the ith component of the reaction
mixture
V = H2 to CO feed ratio
Vm = molar volume (cc)
XCH4 = methane yield
XCO = conversion of carbon monoxide
xi = mole fraction
YCO = mole fraction of CO
YH2 = mole fraction of H2
Z = compressibility factor
-H = heat of reaction (cal/mol of CO)

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