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Cite This: ACS Omega 2019, 4, 22237−22244 http://pubs.acs.org/journal/acsodf

Thermodynamic Equilibrium Analysis of Product Distribution in the

Fischer−Tropsch Process Under Different Operating Conditions
Junjie Chen* and Cheng Yang
Department of Energy and Power Engineering, School of Mechanical and Power Engineering, Henan Polytechnic University, 2000
Century Avenue, Jiaozuo, Henan 454000, P. R. China

ABSTRACT: Thermodynamic equilibrium analysis is necessary to

provide a fundamental understanding of the distribution of the
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products formed in the Fischer−Tropsch process. The thermody-

namic equilibrium distribution of the products formed at constant
temperature and pressure was studied based on the minimization of
the total Gibbs free energy of the system. The effects of
temperature, pressure, and feed ratio on the product distribution
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were investigated under typical operating conditions. The

distribution of the total products obtained from the reactions of
added ethylene or ethanol was also studied. The results indicated
that the products formed in a state of thermodynamic equilibrium
follow Anderson−Schulz−Flory’s general polymerization distribu-
tion at carbon numbers greater than about three. Both olefins and
paraffins are primary products and there are essentially no alcohol and water at high degrees of conversion when the conditions
for thermodynamic equilibrium are satisfied. The olefins formed in the Fischer−Tropsch process consist essentially of
propylene. The product distribution is very sensitive to feed composition, and to temperature and pressure to a lesser extent.
The product spectrum can be described broadly by the probability of chain growth relative to chain termination. This parameter
decreases with increasing temperature, the feed ratio of hydrogen to carbon monoxide, and after the addition of ethanol to the
feed, but increases with increasing pressure and after the addition of ethylene to the feed. An increase in reaction temperature
results in a shift in selectivity towards low carbon number hydrocarbons and more hydrogenated products.

1. INTRODUCTION the catalytically active materials for the Fischer−Tropsch

As the major component of natural gas, methane has attracted process. Cobalt and ruthenium are particularly effective for the
increasing attention in recent years. The primary chemical catalytic conversion of synthesis gas to primary hydrocarbons
reactions of methane are steam reforming to synthesis gas, having five or more carbon atoms.23,24
oxidation, and halogenation.1,2 The quest for an efficient The main products formed in the Fischer−Tropsch process
process to convert methane efficiently to high value-added range from methane to higher alkanes and aliphatic
chemicals is motivated by the ever-increasing demands placed alcohols.25,26 The process is critical to the production of liquid
on them as well as recently discovered rich reserves of fuels and chemicals from carbonaceous feedstock.27,28 Despite
methane. Direct conversion into high value-added chemicals the research that has been done to date, the need exists for
can be realized either nonoxidatively via methane dehydroar- further improvement in commercial Fischer−Tropsch pro-
omatization3,4 or oxidatively via oxidative coupling of cesses.29,30 For example, a great deal of effort has been made to
methane.5,6 Alternatively, methane can be catalytically develop more efficient Fischer−Tropsch reaction systems and
converted to C2 and higher hydrocarbons via an indirect catalyst systems, which will eventually lead to an increase in the
route, and this process is usually carried out in two steps. selectivity for high-value hydrocarbon products from the
Methane is converted into synthesis gas containing carbon Fischer−Tropsch processes.31,32 In particular, iron, cobalt,
monoxide and hydrogen in a steam reforming process or in a and ruthenium based catalysts have been developed for use in
partial oxidation process,7,8 followed by final conversion to various reactor types,33,34 and much progress has been made in
higher hydrocarbons. Synthesis gas can also be produced from preparation technology.35,36
other sources, such as coal, biomass, and virtually any There is a significant difference in the distribution of the
hydrocarbon feedstock, by reaction with steam, oxygen, or hydrocarbon products formed from different Fischer−Tropsch
carbon dioxide.9,10 The production of hydrocarbons from reaction systems.37,38 The selectivity to the desired product
synthesis gas is usually referred to as the Fischer−Tropsch depends upon the conditions under which the Fischer−
process.11,12 Catalysts used in this process are typically
comprised of a catalytically active metal from one of Group Received: November 1, 2019
VIIIB elements.13,14 In particular, iron,15,16 cobalt,17,18 Accepted: November 26, 2019
nickel,19,20 and ruthenium21,22 have been extensively used as Published: December 9, 2019

© 2019 American Chemical Society 22237 DOI: 10.1021/acsomega.9b03707

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Tropsch process is performed.39,40 Accordingly, it is highly

desirable to improve the selectivity to the desired high-value
liquid fuels and chemicals, such as primarily hydrocarbons
having five or more carbon atoms. These hydrocarbons, which
correspond to gasoline or diesel products, are expected to be in
great demand. Traditional methods produce a range of
hydrocarbon products,41,42 which can be characterized by the
Anderson−Schulz−Flory distribution, irrespective of catalyst
type.43,44
Recent studies suggested that thermodynamic equilibrium
analysis is necessary to provide a fundamental understanding of
the distribution of the products formed in the Fischer−
Tropsch process, and the importance of such a product
distribution should not be underestimated.45,46 This thermo- Figure 1. Distribution of the total products at different temperatures.
dynamic method offers greater flexibility for complex problems The logarithm of the mole fraction of the total organic products is
for which the pathways of the Fischer−Tropsch reactions are plotted against the carbon number. The temperatures of the product
unclear. Furthermore, this thermodynamic equilibrium dis- mixture are 510, 525, and 540 K, respectively, the pressure is 1.5 MPa,
and the usage ratio is 0.7.
tribution may have important implications for the improve-
ment in the selectivity of the desired products. However,
selectivity towards low carbon number hydrocarbons, as
further studies are needed to determine the distribution of the
depicted in Figure 1. This shift in selectivity is consistent
Fischer−Tropsch products formed in a state of thermody-
with the relative stability of the products. Therefore, low
namic equilibrium.
carbon number hydrocarbons are thermodynamically favored
In this study, the thermodynamic equilibrium distribution of
at high temperatures. Chain growth probability is somewhat
the products formed in the Fischer−Tropsch process was
sensitive to the reaction temperature. More specifically, this
investigated at constant temperature and pressure. The effects
parameter decreases from 0.72 to 0.68 when the temperature
of different operating conditions on product distribution were
of the thermodynamic equilibrium system increases from 510
evaluated using a thermodynamic equilibrium calculation on
to 540 K. Chain growth probability decreases with increasing
the basis of the minimization of the Gibbs free energy. The
temperature, which is in consistence with the experimental
distribution of the total products obtained from the reactions
results available in the literature.47,48 In addition, the ratio of
of added ethylene or ethanol was also studied. The objective of
the amount of C3 product to that of C2 product increases with
this study was to determine the thermodynamic equilibrium
increasing temperature, which is also in consistence with the
distribution of the products formed in the Fischer−Tropsch
experimental results available in the literature.47,48 This ratio
process under different operating conditions. Particular
indicates the extent of the reincorporation of C2 product.47,48
emphasis was placed on determining how the carbon number
The Fischer−Tropsch reactions are assumed to be carried
product distribution depends on various operating conditions.
out under different pressure conditions, and the effect of
changing pressure on the distribution of Fischer−Tropsch
2. RESULTS AND DISCUSSION
products is investigated. The results obtained for different
The primary compounds involved in the products may be pressures are presented in Figure 2, wherein the distribution of
primary olefins in the C2−C15 range,47,48 normal paraffins in
the C1−C15 range, normal alcohols in the C1−C8 range, water,
and carbon dioxide.49,50 In all of the cases studied herein,
complete conversion of carbon monoxide and hydrogen is
assumed, and all the products are in the vapor phase. The
effects of different operating conditions on product distribu-
tion are investigated under typical operating conditions using
the equilibrium modeling method described later.
2.1. Effects of Temperature and Pressure. The effect of
changing temperature on the distribution of Fischer−Tropsch
products is studied. The results obtained for different
temperatures are presented in Figure 1, wherein the
distribution of the product is expressed as a function of the
number of carbon atoms. The temperatures of the product
mixture considered here are 510, 525, and 540 K, respectively,
Figure 2. Distribution of the total products at different pressures. The
the pressure is 1.5 MPa, and the usage ratio is 0.7. The usage temperature of the product mixture is 540 K, the usage ratio is 0.7,
ratio typically varies between 0.5 and 1.0 for iron-based and the pressures are 0.38, 0.75, and 1.5 MPa, respectively.
catalysts and has been found to be about 0.7, obtained from
the majority of the results available.51,52 The logarithm of the
mole fraction of the total organic products is plotted against the product is expressed as a function of the number of carbon
the number of carbon atoms. atoms. The temperature of the product mixture is 540 K, and
At each temperature of the thermodynamic equilibrium the usage ratio is 0.7. The pressures used in the Fischer−
system, there is a linear relationship between the number of Tropsch process are 0.38, 0.75, and 1.5 MPa, respectively, and
carbon atoms and the concentration of the C4 plus products. thus pressure variations are significant. The results indicate that
An increase in reaction temperature results in a shift in high carbon number hydrocarbons are thermodynamically
22238 DOI: 10.1021/acsomega.9b03707
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favored at high pressures. Chain growth probability is whole system is at thermodynamic equilibrium at the specified
somewhat sensitive to pressure. More specifically, this temperature and pressure, the selectivity to methane is
parameter varies from 0.56 at a pressure of 0.38 MPa to 0.68 between 0.4 and 0.6 in the Fischer−Tropsch product stream.
at a pressure of 1.5 MPa. The selectivity to methane depends on the conditions under
Irrespective of the temperatures and pressures considered which the Fischer−Tropsch process is performed, for example,
herein, the products formed in a state of thermodynamic the feed ratio of hydrogen to carbon monoxide, as depicted in
equilibrium follow Anderson−Schulz−Flory’s general polymer- Figure 3. An increase in the feed ratio of hydrogen to carbon
ization distribution at carbon numbers greater than about monoxide results in a shift in selectivity toward low carbon
three, as predicted in Figures 1 and 2. The Fischer−Tropsch number hydrocarbons, especially towards methane. In all of
synthesis may be viewed as a simple polymerization reaction, the cases studied herein, complete conversion of carbon
and the monomer is carbon monoxide or a C1 species derived monoxide and hydrogen is assumed, as described above. Under
from it. Schulz53,54 derived an equation for the distribution of the specified conditions, the selectivity to methane is relatively
molecular weights of polymers obtained by a free radical low due to low feed ratios of hydrogen to carbon monoxide
polymerization process, i.e., through a one-by-one addition of used in this study. This has important implications for the
monomer to a growing chain. If there is a constant probability improvement in the selectivity of the desired products. Higher
of chain growth, the Schulz distribution function is generally feed ratios of hydrogen to carbon monoxide tend to favor the
applicable. Flory55 and Anderson56 continued efforts to formation of methane, i.e., methanation, as depicted in Figure
account for the products formed by chain branching, to derive 3. This is particularly undesirable. For practical applications,
theoretical distribution functions for various types of macro- however, a variety of feed ratios can be used for the Fischer−
molecular formation, and to develop chain growth mecha- Tropsch process.11,12 The optimum feed ratio of hydrogen to
nisms. The polymerization process can be described by the carbon monoxide is about 1.8−2.1 for cobalt-based cata-
Anderson−Schulz−Flory distribution if the chain growth lysts.13,14 Iron-based catalysts can tolerate lower feed ratios due
probability is assumed to be independent of the chain length. to intrinsic water−gas shift reaction activity of iron-based
2.2. Effect of Feed Ratio. The usage ratio defined in eq 1 catalysts.57,58 Nickel-based catalysts can also be used, but tend
is equal to the feed ratio of hydrogen to carbon monoxide, as a to favor the formation of methane,59,60 especially under high-
complete conversion of hydrogen and carbon monoxide is feed ratio conditions.
assumed in the Fischer−Tropsch process. The results obtained 2.3. Formation of Alcohols and Water. The amount of
for different feed ratios are presented in Figure 3, wherein the alcohols formed in the Fischer−Tropsch process is predicted
by Newton’s method. Interestingly, the products resulting from
the Fischer−Tropsch synthesis contain essentially no alcohols
at high degrees of conversion, when the conditions for
thermodynamic equilibrium are satisfied for the reaction
system. Therefore, alcohols are not favored as products
under the specified conditions, and the product distribution
depicted in Figure 3 is entirely that of normal paraffins and
primary olefins. This offers an explanation for the results
available in the literature,47,48 in which the amount of alcohol
formed in the Fischer−Tropsch process has been found to
decrease with decreasing space velocity. It is worth noting that
low space velocities enable the distribution of the products to
approach chemical equilibrium.
When the conditions for thermodynamic equilibrium are
Figure 3. Distribution of the total products at different feed ratios of satisfied, the amount of water predicted by Newton’s method is
hydrogen to carbon monoxide. The temperature of the product essentially zero at high degrees of conversion. It has been
mixture is 540 K, the pressure is 1.5 MPa, and the feed ratios are 0.6, found that only a small amount of water formed over an iron-
0.7, and 0.8, respectively. based catalyst,47,48 as it is apparently limited by the water−gas
shift reaction. This reaction favors the formation of hydrogen
distribution of the product is expressed as a function of the and carbon dioxide rather than that of carbon monoxide and
number of carbon atoms at a specified temperature and water vapor at the temperatures considered here, given the fact
pressure. The temperature of the product mixture is 540 K, the that the conversion of reactants to products becomes less
pressure is 1.5 MPa, and the feed ratios of hydrogen to carbon favorable with increasing reaction temperature61,62 due to the
monoxide considered here are 0.6, 0.7, and 0.8, respectively. exothermic nature of the Fischer−Tropsch reactions.
There is difference in the distribution of the products 2.4. Formation of Olefins. The amount of olefins formed
formed under different feed ratio conditions, as depicted in in the Fischer−Tropsch process will vary depending on the
Figure 3. For each feed ratio of hydrogen to carbon monoxide, way in which the process is carried out.47,48 To better
there is a linear relationship between the number of carbon understand the distribution of the products, the effect of the
atoms and the concentration of the C4 plus products. reaction temperature is investigated on the basis of the
Corresponding to each feed ratio, chain growth probability is minimization of the Gibbs free energy. The predicted mole
determined based on the C4 plus products. Chain growth fractions of olefins at each carbon number as a function of the
probability is very sensitive to feed ratio. This parameter number of carbon atoms at different temperatures are depicted
decreases from 0.76 at a usage ratio of 0.6−0.58 at a usage ratio in Figure 4. The temperatures of the product mixture
of 0.8. Chain growth probability is 0.68 at a usage ratio of 0.7, considered here are 525 and 540 K, respectively, the pressure
which is the average reported in the literature.51,52 When the is 1.5 MPa, and the usage ratio is 0.7.
22239 DOI: 10.1021/acsomega.9b03707
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Figure 4. Olefin mole fractions obtained at each carbon number at Figure 5. Distribution of the total products after the addition of
different temperatures. The temperatures of the product mixture are ethylene to the feed. The temperature of the product mixture is 540
525 and 540 K, respectively, the pressure is 1.5 MPa, and the usage K, the pressure is 1.5 MPa, and the usage ratio is 0.7.
ratio is 0.7.
Overall, ethylene acts as an effective chain initiator, as the
presence of ethylene enhances the formation of high carbon
The results indicate that Fischer−Tropsch products contain number hydrocarbons.
a certain amount of olefins, in all of the cases studied herein, On the other hand, the effect of the addition of ethanol to
with the amount dependent to some extent on the conditions the feed on the distribution of the total products is depicted in
used. The low carbon number hydrocarbons formed in the Figure 6. Low carbon number hydrocarbons become more
Fischer−Tropsch process are fairly olefinic. The products
contain varying amounts of olefins depending on the
temperature employed. An increase in reaction temperature
results in a shift in selectivity towards more hydrogenated
products, as depicted in Figure 4. This shift is consistent with
the relative stability of the products. The amount of olefins
present in the products is quite different from each other. The
concentration of C2 olefinic products is low, the concentration
of C3 olefinic product is high, and the concentration of high-
molecular-weight olefinic products in the C4−C10 range is
essentially constant. Therefore, the olefins formed in the
Fischer−Tropsch process are predominantly primary olefins,
consisting essentially of propylene, under the specified
conditions. On the other hand, the amounts of olefins decrease
with decreasing temperature. Therefore, higher temperature
operation favors an olefinic product. Figure 6. Distribution of the total products after the addition of
ethanol to the feed. The temperature of the product mixture is 540 K,
2.5. Effect of Ethylene or Ethanol to the Feed. There
the pressure is 1.5 MPa, and the usage ratio is 0.7.
exists evidence that some species such as olefins and alcohols
may become incorporated into growing chains,63,64 but the
extent to which this occurs seems to vary greatly with reaction
conditions.65,66 The distribution of the total products formed thermodynamically favorable after the addition of ethanol to
in the Fischer−Tropsch reactions of added ethylene or ethanol the feed, and the presence of ethanol enhances the conversion
is studied using the equilibrium modeling method described of carbon monoxide to methane through hydrogenation. In
later. addition, the presence of ethanol also affects the chain growth
When the reaction system is in a state of thermodynamic probability. More specifically, this parameter varies from 0.68
equilibrium, the effect of the addition of ethylene to the feed in the absence of ethanol to 0.56 with a molar ratio of ethanol
on the distribution of the total products is depicted in Figure 5. to carbon monoxide 0.2:1. Therefore, chain growth probability
The temperature of the product mixture is 540 K, the pressure is also very sensitive to the addition of ethanol to the feed.
is 1.5 MPa, and the usage ratio is 0.7. High carbon number After the addition of a small amount of ethanol to the feed of
hydrocarbons become more thermodynamically favorable after carbon monoxide and hydrogen, however, the formation of
the addition of ethylene to the feed, and the presence of alcohols with greater than two carbons is enhanced in the
ethylene suppresses the conversion of carbon monoxide to Fischer−Tropsch process. This is because ethanol also acts as a
methane through hydrogenation. Both of them are in chain-growth initiator.69,70 Overall, the distribution of the total
consistence with the experimental data available in the products is greatly affected by the addition of ethylene or
literature.67,68 In addition, the presence of ethylene effects ethanol to the feed.
the chain growth probability. More specifically, this parameter
varies from 0.68 in the absence of ethylene to 0.8 with a molar 3. CONCLUSIONS
ratio of ethylene to carbon monoxide 0.2:1. Therefore, chain The thermodynamic equilibrium distribution of the products
growth probability is very sensitive to the addition of ethylene formed in the Fischer−Tropsch process was studied based on
to the feed. The addition of ethylene to the feed of carbon the minimization of the Gibbs free energy. The following
monoxide and hydrogen enhances the formation of propylene. major conclusions can be drawn from this study.
22240 DOI: 10.1021/acsomega.9b03707
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• The products formed in a state of thermodynamic equilibrium analysis is performed to determine the distribution
equilibrium follow Anderson−Schulz−Flory’s general of the products formed in the Fischer−Tropsch process under
polymerization distribution at carbon numbers greater different operating conditions. The flexibility of the equili-
than about three. brium modeling method used in this study is due to the ease
• Both olefins and paraffins are primary products. The with which the distribution of the products formed in the
olefins formed in the Fischer−Tropsch process are complex reaction system can be determined without needing
predominantly primary olefins, consisting essentially of to specify each chemical reaction equation, as noted above.
propylene. When the conditions for all mechanical, chemical, and thermal
• Product distribution and chain-growth probability are equilibrium are satisfied, the reaction system is in a state of
very sensitive to feed composition, and to reaction thermodynamic equilibrium.77,78 Therefore, the intensive
temperature and pressure to a lesser extent. An increase properties of the product mixture are homogeneous. Global
in the reaction temperature results in a shift in selectivity thermodynamic equilibrium is assumed in this study, and thus
towards low carbon number hydrocarbons and more intensive properties such as temperature, pressure, concen-
hydrogenated products. tration, and density are homogeneous throughout the whole
• The presence of ethylene or ethanol greatly affects the thermodynamic system.
chain growth probability and both of them function as The important criterion for chemical equilibrium is that the
chain initiators. Gibbs free energy is minimized for the overall chemical
• Chain growth probability decreases with increasing reaction proceeded at constant temperature and pressure.
temperature and the feed ratio of hydrogen to carbon Therefore, the Fischer−Tropsch reactions are assumed to be
monoxide but increases with increasing pressure. This carried out at constant temperature and pressure. It is possible
parameter decreases after the addition of ethanol to the to determine the distribution of the products formed in the
feed, but increases after the addition of ethylene to the Fischer−Tropsch process, based on the thermodynamic
feed. equilibrium at which the Gibbs free energy for the overall
• Alcohols and water are thermodynamically unfavored at chemical reaction is minimized. To determine this distribution,
high degrees of conversion when the conditions for it is required to minimize the total Gibbs free energy of the
thermodynamic equilibrium are satisfied. product mixture at thermodynamic equilibrium:
∞
It is worth noting that a general distribution has been
determined for the total products formed in the Fischer− G= ∑ NG
i i
Tropsch process, which is completely independent of the i=1 (2)
reaction mechanism and catalyst used. This general distribu- in which G is the total Gibbs free energy of the product
tion is important to identify the difference in performance mixture at thermodynamic equilibrium under the particular
between different catalysts, and trends in product selectivity, conditions, Ni is the number of moles of each species, and Gi is
through the comparison with the product distributions the Gibbs free energy of species i in the product mixture.
determined by experiment. The mass balance constraints are given for a single-phase
4. DEVELOPMENT OF THE MODEL reaction by
∞
The chemical mechanism of the Fischer−Tropsch synthesis is
still being debated. This synthesis process involves a series of Mk = ∑ nk ,iNi
chemical reactions, and the overall chemical reaction can be i=1 (3)
expressed as in which Mk is the number of moles of element k fed to the
∞ ∞
thermodynamic reaction system, nk,i is the number of atoms of
CO + U H 2 F ∑ aiCiH2i + ∑ biCiH2i+ 2 element k in species i, and Ni is the moles of species i leaving
i=2 i=1 the system.
∞
To minimize the total Gibbs free energy of the product
+ ∑ ciCiH2i+ 1OH + d H2O + eCO2 mixture, Newton’s method is employed with the NASA
i=1 computer program Chemical Equilibrium with Applications
(1) (CEA) developed by Gordon and McBride.79,80 Thermody-
in which U is the overall usage ratio of the Fischer−Tropsch namic data are included with this program for reaction
reactions, and ai, bi, ci, d, and e are the undetermined products and reactants. The thermodynamic data provided
stoichiometric coefficients of the products formed in the with the CEA program are in the form of least-squares
Fischer−Tropsch process. The products are assumed to be coefficients. These data, in formatted form, are processed by
normal paraffins, primary olefins, normal alcohols, water, and subroutine UTHERM and stored for further use in the
carbon dioxide, as defined in the above equation. Paraffins unformatted form. Thermodynamic data are expressed as
constitute a specific type of reaction product of the Fischer− temperature-dependent values. The amount of data for the
Tropsch synthesis included within the hydrocarbons. Paraffins thermodynamic properties of chemical species involved in the
generally do not react further under conditions applicable to Fischer−Tropsch process is very large. Thermodynamic data
the Fischer−Tropsch synthesis.71,72 are readily available through the CEA program and therefore
Thermodynamic equilibrium analysis is of significant are not provided herein. To obtain the Gibbs free energy of
importance to determine the product distribution, as it can species i in the product mix as defined in eq 2, the ideal gas
provide significant insight into the compositions and properties thermodynamic properties are corrected by using the Soave−
of complex mixtures,73,74 on the basis of the minimization of Redlich−Kwong equation of state.81,82
the Gibbs free energy.75,76 Therefore, thermodynamic The distribution of the products can be represented by
22241 DOI: 10.1021/acsomega.9b03707
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■
Article

Mn = (1 − α)α(n − 1) (4) AUTHOR INFORMATION

Corresponding Author
in which Mn is the mole fraction of all the products having n *E-mail: cjjmmm@163.com; cjj@hpu.edu.cn.
carbon atoms, n is the number of carbon atoms in the chain, ORCID
and α is the probability of chain growth relative to chain Junjie Chen: 0000-0001-8348-4896
termination. Chain growth probability is defined as
Notes
rp The authors declare no competing financial interest.

■
α=
rp + rt (5) ACKNOWLEDGMENTS
in which rp and rt are the rates of propagation and termination, This work was supported by the National Natural Science
Foundation of China (No. 51506048).

■
respectively.
The mole fractions of the products formed in the Fischer−
Tropsch process are usually plotted on a semilogarithmic REFERENCES
scale,83,84 as chain growth probability can be determined from (1) Crabtree, R. H. Aspects of methane chemistry. Chem. Rev 1995,
the slope of such a plot in the following form 95, 987−1007.

i 1 − α yz
log Mn = n log α + logjjj
(2) Schwach, P.; Pan, X.; Bao, X. Direct conversion of methane to

zz
k α {
value-added chemicals over heterogeneous catalysts: Challenges and
prospects. Chem. Rev. 2017, 117, 8497−8520.
(6) (3) Wang, L.; Tao, L.; Xie, M.; Xu, G.; Huang, J.; Xu, Y.
Dehydrogenation and aromatization of methane under non-oxidizing
The logarithmic form of the above equation is a convenient conditions. Catal. Lett. 1993, 21, 35−41.
way to characterize the distribution of the total products (4) Ma, S.; Guo, X.; Zhao, L.; Scott, S.; Bao, X. Recent progress in
because a plot of log Mn is linear with the number of carbon methane dehydroaromatization: From laboratory curiosities to
atoms. promising technology. J. Energy Chem. 2013, 22, 1−20.
Mathematical models are of significant importance in the (5) Lunsford, J. H. The catalytic oxidative coupling of methane.
natural sciences such as chemistry.85 Validation of the model is Angew. Chem., Int. Ed. 1995, 34, 970−980.
carried out by comparing the numerical results with the (6) Mleczko, L.; Baerns, M. Catalytic oxidative coupling of methane-
experimental data available in the literature.86 Validation of a reaction engineering aspects and process schemes. Fuel Process.
mathematical model means that the model within its domain Technol. 1995, 42, 217−248.
(7) York, A. P. E.; Xiao, T.; Green, M. L. H. Brief overview of the
of applicability possesses a satisfactory range of accuracy partial oxidation of methane to synthesis gas. Top. Catal. 2003, 22,
consistent with the intended application of the model.87,88 345−358.
The experimental conditions are given as follows: the (8) Horn, R.; Williams, K. A.; Degenstein, N. J.; Schmidt, L. D.
temperature of the product mixture is 536 K, the pressure is Syngas by catalytic partial oxidation of methane on rhodium:
1.48 MPa, and the feed ratio of hydrogen to carbon monoxide Mechanistic conclusions from spatially resolved measurements and
is 0.7. Computational simulations are carried out with the numerical simulations. J. Catal. 2006, 242, 92−102.
model using the same set of conditions to check the accuracy (9) Rostrup-Nielsen, J. R.; Sehested, J.; Nørskov, J. K. Hydrogen and
of the model by comparison with the experimental data. The synthesis gas by steam- and CO2 reforming. Adv. Catal. 2002, 47, 65−
comparison results are presented in Figure 7, wherein the 139.
distribution of the total products formed in the Fischer− (10) Reyes, S. C.; Sinfelt, J. H.; Feeley, J. S. Evolution of processes
for synthesis gas production: Recent developments in an old
Tropsch process, on the basis of methane-free products, is technology. Ind. Eng. Chem. Res. 2003, 42, 1588−1597.
expressed as a function of the number of carbon atoms. The (11) Schulz, H. Short history and present trends of Fischer-Tropsch
results obtained from the model are in good agreement with synthesis. Appl. Catal., A 1999, 186, 3−12.
the experimental data. (12) Xu, J.; Yang, Y.; Li, Y.-W. Fischer-Tropsch synthesis process
development: Steps from fundamentals to industrial practices. Curr.
Opin. Chem. Eng. 2013, 2, 354−362.
(13) Glasser, D.; Hildebrandt, D.; Liu, X.; Lu, X.; Masuku, C. M.
Recent advances in understanding the Fischer-Tropsch synthesis
(FTS) reaction. Curr. Opin. Chem. Eng. 2012, 1, 296−302.
(14) Biloen, P.; Sachtler, W. M. H. Mechanism of hydrocarbon
synthesis over Fischer-Tropsch catalysts. Adv. Catal. 1981, 30, 165−
216.
(15) Cheng, K.; Ordomsky, V. V.; Virginie, M.; Legras, B.;
Chernavskii, P. A.; Kazak, V. O.; Cordier, C.; Paul, S.; Wang, Y.;
Khodakov, A. Y. Support effects in high temperature Fischer-Tropsch
synthesis on iron catalysts. Appl. Catal., A 2014, 488, 66−77.
(16) Wezendonk, T. A.; Sun, X.; Dugulan, A. I.; van Hoof, A. J. F.;
Hensen, E. J. M.; Kapteijn, F.; Gascon, J. Controlled formation of iron
carbides and their performance in Fischer-Tropsch synthesis. J. Catal.
2018, 362, 106−117.
Figure 7. Comparison of the distribution of the total products formed (17) Iqbal, S.; Davies, T. E.; Morgan, D. J.; Karim, K.; Hayward, J.
in the Fischer−Tropsch process, on the basis of methane-free S.; Bartley, J. K.; Taylor, S. H.; Hutchings, G. J. Fischer Tropsch
products, at each carbon number with the experimental data available synthesis using cobalt based carbon catalysts. Catal.Today 2016, 275,
in the literature.86 The temperature of the product mixture is 536 K, 35−39.
the pressure is 1.48 MPa, and the feed ratio of hydrogen to carbon (18) Rahmati, M.; Huang, B.; Mortensen, M. K.; Keyvanloo, K.;
monoxide is 0.7. Fletcher, T. H.; Woodfield, B. F.; Hecker, W. C.; Argyle, M. D. Effect

22242 DOI: 10.1021/acsomega.9b03707

ACS Omega 2019, 4, 22237−22244
ACS Omega Article

of different alumina supports on performance of cobalt Fischer- (42) Rofer-DePoorter, C. K. A comprehensive mechanism for the
Tropsch catalysts. J. Catal. 2018, 359, 92−100. Fischer-Tropsch synthesis. Chem. Rev. 1981, 81, 447−474.
(19) Enger, B. C.; Holmen, A. Nickel and Fischer-Tropsch synthesis. (43) Puskas, I.; Hurlbut, R. S. Comments about the causes of
Catal. Rev. 2012, 54, 437−488. deviations from the Anderson-Schulz-Flory distribution of the
(20) Barbier, A.; Brum Pereira, E.; Martin, G. A. The role of bulk H Fischer-Tropsch reaction products. Catal. Today 2003, 84, 99−109.
and C species in the chain lengthening of Fischer-Tropsch synthesis (44) Tavakoli, A.; Sohrabi, M.; Kargari, A. Application of Anderson-
over nickel. Catal. Lett. 1997, 45, 221−226. Schulz-Flory (ASF) equation in the product distribution of slurry
(21) Carballo, J. M. G.; Yang, J.; Holmen, A.; García-Rodríguez, S.; phase FT synthesis with nanosized iron catalysts. Chem. Eng. J. 2008,
Rojas, S.; Ojeda, M.; Fierro, J. L. G. Catalytic effects of ruthenium 136, 358−363.
particle size on the Fischer-Tropsch Synthesis. J. Catal. 2011, 284, (45) Norval, G. W. Notes on the issues of equilibrium in the Fischer-
102−108. Tropsch synthesis. Can. J. Chem. Eng. 2008, 86, 1062−1069.
(22) Claeys, M.; van Steen, E. On the effect of water during Fischer- (46) Masuku, C. M.; Hildebrandt, D.; Glasser, D. Olefin pseudo-
Tropsch synthesis with a ruthenium catalyst. Catal. Today 2002, 71, equilibrium in the Fischer-Tropsch reaction. Chem. Eng. J. 2012, 181-
419−427. 182, 667−676.
(23) Iglesia, E.; Soled, S. L.; Fiato, R. A. Fischer-Tropsch synthesis (47) Satterfield, C. N.; Stenger, H. G., Jr. Effect of liquid
on cobalt and ruthenium. Metal dispersion and support effects on composition on the slurry Fischer-Tropsch synthesis. 1. Rate of
reaction rate and selectivity. J. Catal. 1992, 137, 212−224. reaction. Ind. Eng. Chem. Process Des. Dev. 1985, 24, 407−411.
(24) Iglesia, E. Design, synthesis, and use of cobalt-based Fischer- (48) Stenger, H. G., Jr.; Satterfield, C. N. Effect of liquid
Tropsch synthesis catalysts. Appl. Catal., A 1997, 161, 59−78. composition on the slurry Fischer-Tropsch synthesis. 2. Product
(25) Stenger, H. G., Jr.; Askonas, C. F. Thermodynamic product selectivity. Ind. Eng. Chem. Process Des. Dev. 1985, 24, 411−415.
distributions for the Fischer-Tropsch synthesis. Ind. Eng. Chem. (49) Satterfield, C. N.; Huff, G. A., Jr.; Longwell, J. P. Product
Fundam. 1986, 25, 410−413. distribution from iron catalysts in Fischer-Tropsch slurry reactors. Ind.
(26) Donnelly, T. J.; Yates, I. C.; Satterfield, C. N. Analysis and Eng. Chem. Process Des. Dev. 1982, 21, 465−470.
prediction of product distributions of the Fischer-Tropsch synthesis. (50) Davis, B. H. Fischer-Tropsch synthesis: Current mechanism
Energy Fuels 1988, 2, 734−739. and futuristic needs. Fuel Process. Technol. 2001, 71, 157−166.
(27) Dry, M. E. The Fischer-Tropsch process: 1950-2000. Catal. (51) Deckwer, W. D.; Serpemen, Y.; Ralek, M.; Schmidt, B.
Today 2002, 71, 227−241. Modeling the Fischer-Tropsch synthesis in the slurry phase. Ind. Eng.
(28) Dry, M. E. Practical and theoretical aspects of the catalytic Chem. Process Des. Dev. 1982, 21, 231−241.
Fischer-Tropsch process. Appl. Catal., A 1996, 138, 319−344. (52) Deckwer, W. D.; Serpemen, Y.; Ralek, M.; Schmidt, B. On the
(29) Geerlings, J. J. C.; Wilson, J. H.; Kramer, G. J.; Kuipers, H. P. C. relevance of mass transfer limitations in the Fischer-Tropsch slurry
E.; Hoek, A.; Huisman, H. M. Fischer-Tropsch technologyfrom process. Chem. Eng. Sci. 1981, 36, 773−774.
(53) Schulz, G. V. Ü ber die Beziehung zwischen Reaktionsgesch-
active site to commercial process. Appl. Catal., A 1999, 186, 27−40.
(30) Davis, B. H. Fischer-Tropsch synthesis: Overview of reactor windigkeit und Zusammensetzung des Reaktionsproduktes bei
Makropolymerisationsvorgängen [in English: On the relationship
development and future potentialities. Top. Catal. 2005, 32, 143−168.
between reaction speed and composition of the reaction product in
(31) Iglesia, E.; Reyes, S. C.; Madon, R. J.; Soled, S. L. Selectivity
macro-polymerization processes]. Z. Phys. Chem. 1935, 30, 379−398.
control and catalyst design in the Fischer-Tropsch synthesis: Sites,
(54) Schulz, G. V. Ü ber die Verteilung der Molekulargewichte in
pellets, and reactors. Adv. Catal. 1993, 39, 221−302.
hochpolymeren Gemischen und die Bestimmung des mittleren
(32) van Santen, R. A.; Ciobîcă, I. M.; van Steen, E.; Ghouri, M. M.
Molekulargewichtes [in English: On the distribution of molecular
Mechanistic issues in Fischer-Tropsch catalysis. Adv. Catal. 2011, 54,
weights in high polymer mixtures and the determination of the mean
127−187.
molecular weight]. Z. Phys. Chem. 1936, 32, 27−45.
(33) Iliuta, I.; Larachi, F. Fischer-Tropsch synthesis in vertical,
(55) Flory, P. J. Molecular size distribution in linear condensation
inclined and oscillating trickle-bed reactors for offshore floating polymers. J. Am. Chem. Soc. 1936, 58, 1877−1885.
applications. Chem. Eng. Sci. 2018, 177, 509−522. (56) Anderson, R. B. The Fischer-Trospch Synthesis; Kölbel, H.,
(34) Mandić, M.; Dikić, V.; Petkovska, M.; Todić, B.; Bukur, D. B.; Kölbel, H., Ralek, M., Eds.; Academic Press: Inc.: NY, 1984.
Nikačević, N. M. Dynamic analysis of millimetre-scale fixed bed (57) Ponec, V. Some aspects of the mechanism of methanation and
reactors for Fischer-Tropsch synthesis. Chem. Eng. Sci. 2018, 192, Fischer-Tropsch synthesis. Catal. Rev. 1978, 18, 151−171.
434−447. (58) van der Laan, G. P.; Beenackers, A. A. C. M. Kinetics and
(35) Mousavi, S.; Zamaniyan, A.; Irani, M.; Rashidzadeh, M. selectivity of the Fischer-Tropsch synthesis: A literature review. Catal.
Generalized kinetic model for iron and cobalt based Fischer-Tropsch Rev. 1999, 41, 255−318.
synthesis catalysts: Review and model evaluation. Appl. Catal., A (59) Bell, A. T. Catalytic synthesis of hydrocarbons over Group VIII
2015, 506, 57−66. metals. A discussion of the reaction mechanism. Catal. Rev. 1981, 23,
(36) Zhang, Q.; Deng, W.; Wang, Y. Recent advances in 203−232.
understanding the key catalyst factors for Fischer-Tropsch synthesis. (60) Lee, G. V. D.; Ponec, V. On some problems of selectivity in
J. Energy Chem. 2013, 22, 27−38. syngas reactions on the Group VIII metals. Catal. Rev. 1987, 29, 183−
(37) Huff, G. A.; Satterfield, C. N. Evidence for two chain growth 218.
probabilities on iron catalysts in the Fischer-Tropsch synthesis. J. (61) Ratnasamy, C.; Wagner, J. P. Water gas shift catalysis. Catal.
Catal. 1984, 85, 370−379. Rev 2009, 51, 325−440.
(38) Donnelly, T. J.; Satterfield, C. N. Product distributions of the (62) Newsome, D. S. The water-gas shift reaction. Catal. Rev. 1980,
Fischer-Tropsch synthesis on precipitated iron catalysts. Appl. Catal. 21, 275−318.
1989, 52, 93−114. (63) Shi, B.; Davis, B. H. Fischer-Tropsch synthesis: Evidence for
(39) Yang, R.; Zhou, L.; Gao, J.; Hao, X.; Wu, B.; Yang, Y.; Li, Y. chain initiation by ethene and ethanol for an iron catalyst. Top. Catal.
Effects of experimental operations on the Fischer-Tropsch product 2003, 26, 157−161.
distribution. Catal. Today 2017, 298, 77−88. (64) Gaube, J.; Klein, H.-F. Studies on the reaction mechanism of
(40) Muleja, A. A.; Yao, Y.; Glasser, D.; Hildebrandt, D. A study of the Fischer-Tropsch synthesis on iron and cobalt. J. Mol. Catal. A:
Fischer-Tropsch synthesis: Product distribution of the light hydro- Chem. 2008, 283, 60−68.
carbons. Appl. Catal., A 2016, 517, 217−226. (65) Hanlon, R. T.; Satterfield, C. N. Reactions of selected 1-olefins
(41) Wojciechowski, B. W. The kinetics of the Fischer-Tropsch and ethanol added during the Fischer-Tropsch synthesis. Energy Fuels
synthesis. Catal. Rev. 1988, 30, 629−702. 1988, 2, 196−204.

22243 DOI: 10.1021/acsomega.9b03707

ACS Omega 2019, 4, 22237−22244
ACS Omega Article

(66) Shi, B.; Jin, C. Deuterium tracer studies on cobalt catalyzed

Fischer-Tropsch synthesis: Addition of alcohols. Appl. Catal., A 2011,
398, 54−58.
(67) Krishna, K. R.; Bell, A. T. The role of C2 intermediates in
Fischer-Tropsch synthesis over ruthenium. Catal. Lett. 1992, 14,
305−313.
(68) Ekerdt, J. G.; Bell, A. T. Evidence for intermediates involved in
Fischer-Tropsch synthesis over Ru. J. Catal. 1980, 62, 19−25.
(69) Tau, L.-M.; Robinson, R.; Ross, R. D.; Davis, B. H. Oxygenates
formed from ethanol during Fischer-Tropsch synthesis. J. Catal. 1987,
105, 335−341.
(70) Kokes, R. J.; Hall, W. K.; Emmett, P. H. Fischer-Tropsch
synthesis mechanism studies. The addition of radioactive ethanol to
the synthesis gas. J. Am. Chem. Soc. 1957, 79, 2989−2996.
(71) Bartholomew, C. H. Recent technological developments in
Fischer-Tropsch catalysis. Catal. Lett. 1990, 7, 303−315.
(72) Davis, B. H. Fischer-Tropsch Synthesis: Reaction mechanisms
for iron catalysts. Catalysis Today 2009, 141, 25−33.
(73) Jia, G.; He, B.; Ma, W.; Sun, Y. Thermodynamic analysis based
on simultaneous chemical and phase equilibrium for dehydration of
glycerol with methanol. Energy 2019, 188, No. 116021.
(74) Tsanas, C.; Stenby, E. H.; Yan, W. Calculation of simultaneous
chemical and phase equilibrium by the method of Lagrange
multipliers. Chem. Eng. Sci. 2017, 174, 112−126.
(75) Rossi, C. C. R. S.; Cardozo-Filho, L.; Guirardello, R. Gibbs free
energy minimization for the calculation of chemical and phase
equilibrium using linear programming. Fluid Phase Equilib. 2009, 278,
117−128.
(76) Yancy-Caballero, D. M.; Guirardello, R. Thermodynamic
simulation of transesterification reaction by Gibbs energy minimiza-
tion. Fluid Phase Equilib. 2013, 341, 12−22.
(77) Maurer, G. Phase equilibria in chemical reactive fluid mixtures.
Fluid Phase Equilib. 1996, 116, 39−51.
(78) Toikka, A. M.; Jenkins, J. D. Conditions of thermodynamic
equilibrium and stability as a basis for the practical calculation of
vapour-liquid equilibria. Chem. Eng. J. 2002, 89, 1−27.
(79) Gordon, S.; McBride, B. J. Computer Program for Calculation of
Complex Chemical Equilibrium Compositions and Applications I.
Analysis; Report Number: NASA RP-1311; National Aeronautics
and Space Administration, Lewis Research Center: Cleveland, OH,
1994.
(80) McBride, B. J.; Gordon, S. Computer Program for Calculation of
Complex Chemical Equilibrium Compositions and Applications II. User’s
Manual and Program Description; Report Number: NASA RP-1311-
P2; National Aeronautics and Space Administration, Lewis Research
Center: Cleveland, Ohio, 1996.
(81) Redlich, O.; Kwong, J. N. S. On the thermodynamics of
solutions. V. An equation of state. Fugacities of gaseous solutions.
Chem. Rev. 1949, 44, 233−244.
(82) Soave, G. Equilibrium constants from a modified Redlich-
Kwong equation of state. Chem. Eng. Sci. 1972, 27, 1197−1203.
(83) Förtsch, D.; Pabst, K.; Groß-Hardt, E. The product distribution
in Fischer-Tropsch synthesis: An extension of the ASF model to
describe common deviations. Chem. Eng. Sci. 2015, 138, 333−346.
(84) Snel, R. Deviations of Fischer-Tropsch products from an
Anderson-Schulz-Flory distribution. Catal. Lett. 1988, 1, 327−330.
(85) Vigo-Aguiar, J. Mathematical modeling for chemistry-related
applications. J. Math. Chem. 2013, 51, 1135−1138.
(86) Stenger, H. G., Jr. Studies of the Fischer−Tropsch Synthesis in
a Slurry Reactor. Thesis, Doctor of Science; Massachusetts Institute of
Technology, Department of Chemical Engineering: Cambridge, MA,
1984.
(87) Sargent, R. G. Verification and validation of simulation models.
J. Simul. 2013, 7, 12−24.
(88) Banks, J.; Gerstein, D.; Searles, S. P. Modeling Processes,
Validation, and Verification of Complex Simulations: A Survey;
Methodology and Validation, Simulation Series; Society for
Computer Simulation. The Society for Modeling and Simulation
International: San Diego, CA, 1987; Vol. 19, pp 13−18.

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ACS Omega 2019, 4, 22237−22244