ARTICLE

pubs.acs.org/EF

Fischer
Tropsch Synthesis in a Fixed Bed Reactor

Alex Moutsoglou* and Posi Praveen Sunkara
Mechanical Engineering Department, South Dakota State University, Brookings, South Dakota 57007, United States

ABSTRACT: A numerical simulation that models the Fischer
Tropsch (FT) synthesis in a tubular multitube reactor packed with
an iron-based catalyst is conducted to assess the effects of process parameters on product distribution. The study adopts the alkyl and
alkenyl mechanisms in predicting the formation of paraffins and olefins. The effects of the desorbed hydrocarbons on the gaseous
flow and reaction kinetics are accounted for in the computational algorithm. The extent of the variation of the syngas molar feed
ratio, reactor inlet pressure, and reactor length on paraffin and olefin selectivities and mass flow rates is documented. Three distinct
regions of the FT synthesis in the packed tube are documented. In the first region, the polymerization reactions are characterized
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with the absence of termination reactions that result in chain propagation reactions reaching higher carbon atom numbers with
increasing axial length. The beginning of the second region is marked with the initial formation of desorbed species. The second
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region is characterized initially with chain termination reactions reaching higher carbon atom numbers with increasing axial length.
This results in the decrease of the extent of the chain propagation reactions to lower carbon atom numbers, which itself limits the
termination reactions to lower carbon atom numbers. This is the only region where liquid olefin and paraffins are formed, as the end
of the second region is marked with the propagation reactions not reaching carbon number atoms beyond n = 19. In the third region,
with the chain propagation reactions keep diminishing to lower carbon atom numbers, the termination reactions themselves
decrease to lower carbon atom numbers. This region is characterized with constant gas flow rates, as in the absence of desorbed
liquids any decrease in syngas results in the formation of low carbon number gaseous olefins and paraffins.

’ INTRODUCTION As the desired products are the heavier hydrocarbons, the FT

Conversion of lignocellulosic feedstock into transportation fuels
is a topic that is currently being studied quite extensively. The main
conversion processes in achieving this are fast pyrolysis and
Fischer
Tropsch (FT) synthesis. Both processes have been shown
to be viable procedures in converting biomass to liquid fuels.
The three major processes in the FT technology are synthesis
gas preparation, FT synthesis, and product upgrading. Current
interest is in producing syngas from gasification of lignocellulosic
feedstock. FT synthesis can proceed at either low temperatures
(200
240 °C, LTFT) using an iron or cobalt catalyst or high
temperatures (300
350 °C, HTFT) using an iron catalyst.
Slurry and fixed bed reactors are typically used in LTFT, while
fluidized bed reactors are common in HTFT.
The thermochemistry taking place in an FT reactor is complex
but can be generalized as follows:1
Methanation Reaction
CO þ 3H2 f CH4 þ H2 O
Fischer
Tropsch (FT) Reaction
nCO þ 2nH2 f ð
CH2
Þn þ nH2 O
Alcohol Formation
nCO þ 2nH2 f Cn H2n þ 2 O þ ðn
1ÞH2 O
reaction is predominant. It is noted that the FT reaction models
only the formation of olefins but not paraffins. The extent of the
WGS reaction depends on the bed catalyst. Generally, for cobalt
catalysts the extent of the WGS reaction is negligible, and this
reaction may be treated as a one way reaction producing a small
amount of carbon dioxide. On the other hand, for iron catalysts at
high temperatures, the WGS reaction approaches equilibrium. In
this case, the direction of the WGS reaction depends on the gas
composition.
In the FT synthesis, the H2 to CO ratio (consumption or
usage ratio) for cobalt catalysts is determined primarily by the FT
reaction, with a significant influence from the methanation
reaction. In these instances, the usage ratio typically ranges from
2.06 to 2.16. For iron catalysts, when the WGS reaction is in
equilibrium, the combined usage ratio for the FT and WGS
reactions is difficult to pin down and depends on the feed gas
composition and can dip below 2. For the forward shift reaction
the combined usage ratio is 0.5.
ð1Þ Conversion can be expressed as the rate of consumption of
CO þ H2. As the CO and H2 are in opposite sides of the WGS
reaction, the rate of consumption of CO þ H2 is independent of
the extent of the WGS reaction. A more useful concept in
ð2Þ expressing conversion is in terms of the rate of consumption of
CO þ CO2. This approach is valid even if CO2 is produced rather
than consumed. It is also independent of the extent of the WGS
reaction as CO and CO2 are in opposite sides of the equation.
ð3Þ With this approach, the amount of carbon in the products can be

Water
Gas Shift (WGS) Reaction Received: January 29, 2011

Revised: March 21, 2011
CO þ H2 O T CO2 þ H2 ð4Þ Published: March 22, 2011

r 2011 American Chemical Society 2242 dx.doi.org/10.1021/ef200160x | Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
directly equated to the amount of carbon consumed. This is not
the case for the CO þ H2 conversion, where in addition one
needs to know the ratio of carbon to hydrogen and oxygen in the
products.
In order to describe the distribution of the products produced
by the FT process, the product selectivity is utilized. The product
selectivities are best expressed on a carbon atom basis. Thus, for a
hydrocarbon CnHm, the carbon atom selectivity Sn is defined
from
moles of Cn Hm producedn
Sn ¼ ð5Þ
total moles of C converted
Product selectivities can also be expressed on a mass basis
of the total carbon products. As most hydrocarbon products
are made up of methylene “CH2” building blocks, the carbon
atom selectivities and mass selectivities result in similar
numbers except for low molecular alkanes and oxygenated
compounds. It is more convenient to express the product
selectivities on a carbon atom basis, and that is the approach
taken in this study.
An important design factor in the overall FT process is the
matching of the H2/CO ratio in the syngas composition to the
usage ratio of the FT synthesis process. The usage ratio itself
depends on the overall product selectivity, which in turn depends
on several factors in the reactor. The FT reaction produces a wide
range of hydrocarbon and oxygenated hydrocarbon atoms. In
one extreme, the selectivity of methane can vary from 1 to 100%,
while on the other end, the selectivity of long chain linear waxes
can vary from 0 to 70%. The intermediate carbon number
products between these extremes are only produced in limited
amounts.
’ FT REACTION MECHANISMS
The FT synthesis is a polymerization reaction where the
monomers CH2 are formed on the catalyst surface from
the gaseous reactants hydrogen and carbon monoxide. All
proposed reaction pathways in the FT synthesis include
(i) chain initiation, (ii) chain propagation, and (iii) chain termi-
nation. A model that combines the alkyl and alkenyl mechan-
isms in simulating the FT reaction pathways is adopted in this
study.1
According to the alkyl mechanism, chain initiation takes
place via dissociative CO chemisorption that generates sur-
face carbon and surface oxygen. Subsequently, surface oxygen
is removed from the surface by reaction with adsorbed
hydrogen yielding H2 O or with adsorbed carbon monoxide
yielding CO2, while surface carbon is hydrogenated to form
successively “CH” (methylidyne), the monomer “CH2”
(methylene), and the chain initiator “CH3” (methyl) on the
catalyst surface
•
CH2 þ • H f Rð1Þ chain initiation ð6Þ
where the alkyl group R(n) = CnH2nþ1 and R(1) = CH3.
Chain propagation takes place by successive incorporation of
methylene to alkyl groups.
•
RðnÞ þ CH2 f Rðn þ 1Þ n ¼ 1, 2, 3, ::: chain propagation
ð7Þ
2243
ARTICLE
Thus, the methyl group changes to ethyl, the ethyl to n-propyl, the n-
propyl to n-butyl, and so on. Chain termination occurs by either
reduction to form n-paraffins (alkanes), P(n) = CnH2nþ2
RðnÞ þ • H f PðnÞ n ¼ 2, 3, 4, ::: chain termination to n-paraffins
ð8Þ
or via β-hydride abstraction to form R-olefins, E(n) = CnH2n.
RðnÞ f EðnÞ þ • H n ¼ 3, 4, 5, ::: chain termination to R-olefins
ð9Þ
In the alkenyl mechanism, the chain initiator is taken to be a
vinyl surface group CHdCH2 which forms through the coupling
of methylidyne CH and methylene CH2
•
CH þ • CH2 f Q ð2Þ chain initiation ð10Þ
where the alkenyl group Q(n) = CnH2n
1 and Q(2) = C2H3.
Chain propagation takes place by successive incorporation of
methylene to alkenyl groups.
Q ðnÞ þ • CH2 f Q ðn þ 1Þ n ¼ 2, 3, 4, ::: chain propagation
ð11Þ
Thus, the vinyl group C2H3 changes to allyl C3H5, the allyl to
butenyl C4H7, and so on. Chain termination occurs by surface
reduction of an alkenyl species to yield R-olefins.
Q ðnÞ þ • H f EðnÞ n ¼ 3, 4, 5, ::: chain termination to R-olefins
ð12Þ
The alkenyl mechanism fails to explain the primary formation of
n-paraffins.
Methane and ethylene are formed by reactions that do not
involve propagating species and therefore are governed by
different reactions. Methane is formed by termination of methyl
•
CH3 which reacts with surface hydrogen at a higher rate than
termination of R(n) species when n > 2.
Rð1Þ þ • H f Pð1Þ ð13Þ
Ethylene is formed by the reaction of two methylene species
rather than termination of an R(2) or Q(2) species.
•
CH2 þ • CH2 f Eð2Þ ð14Þ
The alkyl mechanism does not form ethylene as there is a stable
methyl
CH3 at the end of the propagating species. Neither the
alkyl nor the alkenyl mechanisms are able to explain the forma-
tion of oxygenates in the FT synthesis.
The carbon number product distribution depends on several
operating factors including reactor temperature and pressure, the
kind of catalyst used, the amount and type of promoter present,
and the reactor type. The main products of the FT synthesis
are R-olefins and n-paraffins, along with some oxygenate and
branched compounds. Several mathematical models have been
developed in predicting the FT product distribution. The
simplest basic model depicting the stepwise chain growth con-
cept is that of Anderson
Schulz
Flory distribution given as
wi ¼ Ri
1 ð1
RÞ2 i ð15Þ
where, wi is the mass fraction of the ith carbon number and R is
the chain growth probability.
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels ARTICLE

’ COMPUTATIONAL ALGORITHM With the above simplifications, the system of eqs 16
24 can be
In the present study, a fixed bed vertical multitube reactor filled with rewritten as
iron catalyst is considered for the FT synthesis. Synthesis gas with a ki pH2
known H2/CO molar ratio and inlet pressure pi is forced through the Rð1Þ ¼ ð26Þ
kp
tubes of length L, which are maintained at a temperature T. The pressure
at the exit of the reactor is kept at a constant value of pe. kp RFTS
A kinetic model developed by Fernandes2 that is based on the alkyl RðnÞ ¼ Rðn
1Þ n ¼ 2, 3, 4, ::: ð27Þ
and alkenyl mechanisms described earlier is adopted. For the alkyl kp RFTS þ kpar pH2 þ kolef
mechanism, mass balances for eqs 6
9 result in
dPð1Þ kmet pH2
dRð1Þ ¼ Rð1Þ ð28Þ
¼ ki ½• CH2 ½• H
kp ½• CH2 Rð1Þ ð16Þ dz u
dt
dPð2Þ ket pH2
dRðnÞ ¼ Rð2Þ ð29Þ
¼ kp ½• CH2 Rðn
1Þ
kp ½• CH2 RðnÞ dz u
dt

kolef RðnÞ
kpar ½• HRðnÞ n ¼ 2, 3, 4, ::: ð17Þ dPðnÞ kpar pH2
¼ RðnÞ n ¼ 3, 4, 5, ::: ð30Þ
dz u
dPðnÞ
¼ kpar ½• HRðnÞ n ¼ 2, 3, 4, ::: ð18Þ ki2 RFTS
dt Q ð2Þ ¼ ð31Þ
kp2
dEðnÞ
¼ kolef RðnÞ n ¼ 3, 4, 5, ::: ð19Þ kp2 RFTS
dt Q ðnÞ ¼ Q ðn
1Þ n ¼ 3, 4, 5, ::: ð32Þ
kp2 RFTS þ kolef 2
Similarly for the alkenyl mechanism, mass balances for eqs 10
12
result in
dEð2Þ kO RFTS 2
dQ ð2Þ ¼ 2 ð33Þ
¼ ki ½• CH2 ½• CH2 
kp2 ½• CH2 Q ð2Þ ð20Þ dz u
dt
dEðnÞ kolef RðnÞ þ kolef 2 Q ðnÞ
dQ ðnÞ ¼ n ¼ 3, 4, 5, ::: ð34Þ
¼ kp2 ½• CH2 Q ðn
1Þ
kp2 ½• CH2 Q ðnÞ dz u
dt
where the olefin productions from the alkyl and alkenyl mechanisms
n ¼ 3, 4, 5, ::: ð21Þ have been combined in eq 34. In eqs 28
30, 33, and 34, the time
derivatives were converted to axial derivatives using d/dt = (d/dz)(dz/
dEðnÞ dt), where dz/dt = u is the local gas superficial velocity at any axial
¼ kolef 2 Q ðnÞ n ¼ 3, 4, 5, ::: ð22Þ
dt location in the bed.
Finally, mass balances for methane and ethylene formation can be To close the system of eqs 26
34 along with eq 25, the partial
written from eqs 13 and 14 to give pressures appearing in these equations need to be established as
a function of position in the reactor. This is achieved by considering
dPð1Þ overall mass balances for the constituents of the synthesis gas flowing
¼ kmet ½• HRð1Þ ð23Þ in the reactor. From the Fischer
Tropsch reaction, eq 2, and the
dt
water
gas reaction, eq 4, the mass conservation of species equations can
dEð2Þ be written as3
¼ kO2 ½• CH2 ½• CH2  ð24Þ
dt
dN_ CO
In the above equations R, P, Q, and E are all in moles per kilogram ¼ Fcat Að
RFTS
RWGS Þ ð35Þ
dz
catalyst.
In the Fischer
Tropsch synthesis, the propagating alkyl and alkenyl dN_ H2
species R(n) and Q(n) are being formed and consumed constantly at ¼ Fcat Að
2RFTS þ RWGS Þ ð36Þ
dz
very fast rates, that leads to the quasi-steady-state assumption that the
concentrations of R(n) and Q(n) can be taken to be constant. This
dN_ H2 O
allows the elimination of the time derivatives in eqs 16, 17, 20, and 21, ¼ Fcat AðRFTS
RWGS Þ ð37Þ
reducing these equations to algebraic form. dz
In the above set of equations the concentrations [•CH2] and [•H] are
dN_ CO2
not directly known. The concentration of methylene is taken to be ¼ Fcat ARWGS ð38Þ
proportional to the well documented overall Fischer
Tropsch reaction dz
rate RFTS of eq 2 given in moles per hour gram catalyst from ·
where N are the species mole flow rates, Fcat is the density of the catalyst,
kFTS pCO pH2 A is the cross-sectional area of the tube in which the gas is flowing, and
RFTS ¼ ð25Þ RFTS given from eq 25 is the overall reaction rate of the FT reaction 2.
pCO þ apH2 O
RWGS is the water
gas reaction rate in moles per hour gram catalyst.
where pCO, pH2, and pH2O are the partial pressures of the reactants and

pCO2 pH2
products of eq 2. The surface hydrogen concentration [•H] is taken to be pCO pH2 O

K1
proportional to its adsorption rate, which can be written in terms of its RWGS ¼ kWGS ð39Þ
partial pressure pH2. ðpCO þ K2 pH2 O Þ2

2244 dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257

Energy & Fuels ARTICLE

Table 1. Kinetic Constants for the Fischer
Tropsch and found following Ergun’s equation5
Water
Gas Reactions in Iron Catalysts4  
dp u 1
φ 150ð1
φÞμ
kFTS 0.39816 mol/h 3 gcat 3 MPa ¼
þ 1:75Fu ð44Þ
dz dcat φ3
dcat
a 3.016
kWGS 0.10512 mol/h 3 gcat
K1 85.81 F is the gas mixture density estimated from the ideal gas law
K2 3.07 pMG
F¼ ð45Þ
RT
Table 2. Kinetic Parameters for CO Polymerization in Iron where the molecular weight of the gas mixture is calculated from
Catalyst2
ki 0.4963 1/MPa MG ¼ yCO MCO þ yH2 MH2 þ yH2 O MH2 O þ yCO2 MCO2
ki2 8.054 h 3 gcat/mol
nG nG
kp
kp2
0.3530 gcat/mol
0.4206 gcat/mol
þ ∑ yk
k¼1
par
Mkpar þ ∑ yk
k¼1
olef
Mkolef ð46Þ

kpar 0.02314 1/h 3 MPa

kolef 0.003487 1/h 3 gcat The mole fractions of the gaseous paraffins and olefins in the gas mixture
kolef2 0.04792 1/h 3 gcat flowing in the packed tube are found from
kmet 0.06386 1/h 3 MPa
N_ ipar
ket 0.02421 1/h 3 MPa yipar ¼
N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2
kO2 0.09994 h 3 gcat2/mol
nG nG

The kinetic constants appearing in the FT and WGS reactions are

þ ∑ N_ k
k¼1
par
þ ∑ N_ k
k¼1
olef
for i e nG ð47Þ

given in Table 1 for iron catalysts from the experiments of Raje and
Davis4 for a reactor temperature of 270 °C, reactor pressure of 1.3 MPa, N_ iolef
yiolef ¼
and molar syngas feed ratios of H2/CO = 0.67 and 1.7. The remaining N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2
kinetic parameters appearing in eqs 26
34 were established by nG nG
Fernandes2 using the empirical data of Raje and Davis4 for iron catalysts
at 270 °C, and are given in Table 2.
þ ∑ N_ k
k¼1
par
þ ∑ N_ k
k¼1
olef
for i e nG ð48Þ

At any axial location z of the reactor tube, the partial pressures can be
and the molecular weights of paraffins and olefins are given as
calculated from the definition of mole fractions:
pCO N_ CO Mkpar ¼ kMC þ ð2k þ 2ÞMH Mkolef ¼ kMC þ 2kMH ð49Þ
yCO ¼ ¼ nG nG
p
N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2 þ ∑ N_ k
k¼1
par
þ ∑ N_ k
k¼1
olef
The viscosity of any gaseous component (except H2O) in the mixture
ð40Þ is estimated using Sutherland’s formula6

 
0:555T0 þ ci T 3=2
pH N_ H2 μi ¼ μ0i ð50Þ
yH2 ¼ 2 ¼ nG nG 0:555T þ ci T0
p
N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2 þ ∑ N_ k
k¼1
par
þ ∑ N_ k
k¼1
olef

where T0 is the reference temperature in Rankine, μ0 is the gas viscosity

ð41Þ
at the reference temperature T0, T is the actual temperature in Rankine,
and c is Sutherland’s constant.7 The viscosity of water vapor is estimated
pH2 O N_ H2 O from ref 8. The viscosity of the gas mixture appearing in eq 44 is then
yH2 O ¼ ¼ nG nG
calculated using the semiempirical formula of Wilke9
p
N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2 þ ∑ N_ k par
þ ∑ N_ k olef
k¼1 k¼1 m yi μi
ð42Þ μ¼ ∑ m
i¼1
j¼1
∑ yi Φij
pCO2 N_ CO2 !
1=2 2 !1=2
 32
yCO2 ¼ ¼ nG nG
μ Mj 1=4 5
p
N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2 þ ∑ N_ k
k¼1
par
þ ∑ N_ k
k¼1
olef Φij ¼
1
8
1þ
Mi
Mj
41 þ i
μj Mi
ð51Þ

ð43Þ
In estimating the viscosity of the gas mixture from eq 51 only the
The summation terms above represent the total mole flow rates of the viscosities of the CO, H2, CO2, and H2O are accounted for in the
gaseous paraffins and olefins desorbed at any axial location z and mixed summations (m = 4).
with the syngas flowing down the tube, while p represents the total The superficial velocity of the gas that appears in eqs 28
30, 33, 34,
pressure at that axial location. In the analysis, paraffins and olefins with and 44 is defined from
carbon number of 19 or less are assumed to be gaseous, thus nG = 19.
The variation of the total pressure with axial location in the reactor m_ G
u  ð52Þ
tube packed with catalyst of diameter dcat and having a porosity φ, is FA

2245 dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257

Energy & Fuels
· ·
where mG is the total mass flow rate of the gaseous products at any axial
position, calculated from
nG
m_ G ¼ ½N_ CO þ N_ H2 þ N_ H2 O þ N_ CO2 þ ∑ N_ k
k¼1
It is noted that the mass flow rate of the gas flowing down the packed
tube changes as CO and H2 adsorb to catalyst surface while desorbed
paraffins and olefins are reintroduced back to the stream, some in
gaseous (n < 20) and some in liquid form (n g 20). In eqs 40
43, 47, 48,
and 53, the mole flow rates of the gaseous paraffins and olefins appear
and need to be determined. The system of kinetic reaction eqs 26
34
provides estimates for the desorbed paraffins and olefins, as well as for
the alkyls R(n) and alkenyls Q(n) on the catalyst, in moles per kilogram
of catalyst. The mole flow rate of the carbon adsorbed on the catalyst is
the rate of carbon conversion at any axial location calculated from
N_ Cdesorbed ¼ ðN_ CO þ N_ CO2 Þz ¼ 0
ðN_ CO þ N_ CO2 Þz
where the mole flow rates of CO and CO2 can be found from solving
eqs 35
38.
Next, from the solution of the system of kinetic eqs 26
34, the
carbon number selectivity, i.e., fraction of carbon atoms present in each
paraffin or olefin (both gaseous and liquids) divided by the total number
of carbon atoms in all paraffins, olefins, and propagating alkyl and alkenyl
species at each axial location can be written as
nPðnÞ
Snpar ¼ nF nF
∑
i¼1
iPðiÞ þ ∑
i¼2
iEðiÞ þ nF RðnF Þ þ nF Q ðnF Þ
paraffins olefins
nEðnÞ
Snolef ¼ nF nF
∑ iPðiÞ þ i∑¼ 2 iEðiÞ þ nF RðnF Þ þ nF Q ðnF Þ
i¼1
paraffins olefins
where nF represents the highest carbon atom accounted for in the
computational simulation. Results presented in this study are for nF = 30.
The mole flow rates of the desorbed paraffins and olefins at each axial
location z can then be construed from
Snpar N_ Cdesorbed
N_ npar ¼
n
Sn N_ C
N_ nolef ¼ olef desorbed
n
The fixed bed reactor for the FT synthesis consists of a multitube
reactor, each tube of diameter dtube and length L, packed with an iron-
based catalyst. Synthesis gas with a known composition is fed at the top
of the reactor and passes through the packed tubes. Water passes outside
of the tubes to cool the gases and maintain the reactor temperature at a
constant value. The reactor pressure at the inlet and exit of the bed are
assumed known.
For the numerical calculations presented in the Results section, the
following values are assigned: tube diameter dtube = 2.5 cm, tube length
L = 2, 2.5, 3, and 3.5 m, apparent catalyst density Fcat = 647 kg/m3,
catalyst diameter dcat = 70 μm, fixed bed porosity φ = 0.6, reactor
temperature T = 270 °C, reactor inlet pressure pi = 3, 3.5, and 4 MPa,
reactor exit pressure pe = 0.1 MPa. Holding the exit pressure constant at
the atmospheric value provides a common basis for independently
assessing the effects of process parameters on product selectivities.
The initial mole fractions of all hydrocarbons in the entering synthesis
gas are taken as zero at the top of the reactor. At the inlet, the mole
fractions of the synthesis gas are assigned the values yH2O = 0, yCO2 = 0,
ARTICLE
and N_ H2/NCO2 = 1, 1.5, and 2. To start solving the system of equations, a
guess for the superficial velocity is made at the top of the reactor. The
nG mole flow rates for CO, H2, CO2, and H2O are then calculated from
par
þ ∑ N_ k
olef
MG
FuA
k¼1
N_ i ¼ yi ð59Þ
ð53Þ MG
with F and MG estimated from eqs 45 and 46, respectively. The partial
pressures of the gaseous mixture are then determined from eqs 40
43.
With RFTS and RWGS calculated from eqs 25 and 39, equations 26
34
along with eqs 35
38 and 44 are solved simultaneously to obtain the
mole per kilogram catalyst of R(n), Q(n), P(n), and E(n), as well as, the
· ·
mole flow rates N_ CO, NH2, N_ H2O, NCO2, and total pressure p, at the new
axial location. Then using eqs 54
58, the mole flow rates of the
desorbed paraffins and olefins are calculated. Treating all paraffins and
olefins with a carbon number less than 20 as gaseous, a new gas mixture
molecular weight, gas density, mass flow rate, and superficial velocity is
estimated from eqs 45
53 for the new axial location. This procedure is
ð54Þ then repeated until the bottom of the reactor is reached, where the
calculated pressure at the exit of the reactor is checked against its known
assigned value of 0.1 MPa. A Newton
Raphson scheme with under-
relaxation is then used to correct the initial guess of the inlet superficial
velocity, and the iterations are continued until the deviation between the
calculated and assigned pressure values at the exit is less than 10
4 MPa.
Numerical results are obtained with up to a carbon number of n = 30.
Numerical tests on the effects of the axial step size employed in the
Runge
Kutta integration are conducted. Axial step sizes of 2 mm (when
L = 2 m) to 3.5 mm (when L = 3.5 m) are determined to be sufficiently
ð55Þ
small for grid independence, where deviations are found to be less
than 0.1%.
’ RESULTS
ð56Þ To validate the computational algorithm, a mass balance is
performed in the reactor. Results for an inlet pressure of 4 MPa, a
reactor length of 3 m, and two H2/CO molar feed ratios of 1.5
and 2 are presented in Table 3. As shown, a mass balance of C
where carbon is counted entering as CO and CO2 and leaving as
CO, CO2, paraffins, and olefins (both as gases and liquids), along
with any carbon propagating as alkyl and alkenyl in the catalyst
results in an exact match within a hundredth accuracy. Paraffins
and olefins up to carbon number 30 are computed in the
ð57Þ algorithm. A corresponding mass balance of monatomic H,
entering as H2 and H2O while leaving as H2, H2O, paraffins,
and olefins (both as gases and liquids), along with any H
ð58Þ propagating as alkyl and alkenyl results in a slight mismatch, as
shown for both cases in the table. This is because of the limitation
of the FT reaction to model the formation of olefins but not
paraffins, resulting in C and H adsorbing to the catalyst always on
a 1 to 2 ratio as predicted by the FT and WGS reactions, eqs 2 and 4.
Although this ratio is maintained in the olefin formation CnH2n,
this is not the case when paraffins CnH2nþ2 are formed. When the
extra hydrogen in paraffins CnH2nþ2 is accounted for, the
differences between entering and exiting masses in the last
column of Table 3 are recovered. A mass balance of O entering
and leaving as CO, CO2, and H2O resulted in a zero error within
two decimal places accuracy. Finally, an overall mass balance for
all species entering and leaving produced exactly the same
balance error as that generated for the balance of H due to the
omission of any CnH2nþ2 in the FT reaction eq 2.
In Table 4, the mole ratio (H/C)utilized calculated by two
different methods, is depicted for the same two cases as those for
Table 3. The (H/C)converted is calculated by taking the ratio of the
H consumed (difference of H entering and leaving as H2 and
2246 dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Table 3. Elemental and Total Mass Balances as Calculated from the Numerical Simulations
entering mass in exiting mass in converted mass in mass in paraffins
syngas [g/h] syngas [g/h] syngas [g/h] produced [g/h] produced [g/h]
pi = 4 MPa, L = 3 m, H2/CO = 2, pe = 0.1 MPa
C 5853.10 2850.41 3002.69 480.93
H 1964.72 1460.76 503.96 105.61
O 7796.69 7796.69
total 15614.52 12107.87 3506.65 586.54
pi = 4 MPa, L = 3 m, H2/CO = 1.5, pe = 0.1 MPa
C 6639.54 3747.06 2892.48 450.18
H 1671.53 1186.07 485.46 97.25
O 8844.28 8844.28
Total 17155.34 13777.41 3377.94 547.43
H2O) to the C consumed (difference of C entering and leaving as
CO and CO2) is found to equal to 2 mol of H per mole of C,
regardless of the feed ratio, reactor length, or inlet pressure. This
is the case, because the C and H on the catalyst first react to form
the monomer CH2, as illustrated by the FT reaction (eq 2), for
both the alkyl and alkenyl mechanisms while not accounting for
the extra two hydrogen atoms formed per mole of paraffin in
CnH2nþ2. The same mole ratio (H/C)synthesized is more accu-
rately calculated from the H and C found in the paraffins, olefins,
alkyls, and alkenyls and is shown to deviate from the ratio of 2
found above, as it truly accounts for all hydrocarbons formed.
The variation of the pressure, gas density, mass flow rate, and
superficial velocity in the packed tube as a function of axial
position in the reactor are shown in Figures 1
5, for a reactor
length of L = 3 m, inlet pressure pi = 4 MPa, and three inlet H2/
CO molar feed ratios of 1, 1.5, and 2.
In Figure 1, the pressure is shown to decrease almost linearly
until near the end of the reactor, where it is seen to drop very
quickly to match the exit pressure. Ergun’s eq 44 dictates that the
pressure gradient is a function of the superficial velocity and the
density. As seen from Figures 2 and 5, both density and super-
ficial velocity vary only slightly in the first part of the reactor,
while both vary drastically near the latter part of the tube. As the
density decreases with decreasing pressure (eq 45), the super-
ficial gas velocity increases to conserve mass. With the mass flow
rate of the gas remaining constant over the latter part of the
reactor (see Figures 3 and 4), the increase in the superficial gas
velocity causes the sharp decrease of the pressure seen in Figure 1.
The variation of the feed ratio does not have any effect on the
pressure distribution, as indicated in Figure 1, although it does
seem to have a pronounced effect on the gas density and mass
flow rates. It is also noted that Ergun’s equation does not account
for the desorbed hydrocarbons that are in the liquid phase
(paraffins and olefins with carbon atom numbers of equal or
greater than 20). One would predict that in the presence of liquid
trickling down the packed tube, the slope of the pressure would
be a greater negative number.
The variation of the gas density with axial location is plotted in
Figure 2. As can be seen from eq 45, for an isothermal reactor, the
density is affected by the pressure and the molecular weight of
the gas. At a constant feed ratio H2/CO, the primary factor is the
pressure, and thus, the density generally follows the trend of
the pressure shown in Figure 1: a slow decrease for about half the
reactor length, followed by a sharp decrease, especially near the
2247
ARTICLE
mass in olefins mass in propagating alkyl total mass mass balance
and alkenyl [g/h] synthesized [g/h] in
out [g/h]
2521.76 9.58  10
12 3002.69 0
423.24 1.64  10
12 528.86
24.90
0
2945.00 1.12  10
11 3531.54
24.90
2442.29 1.72  10
11 2892.48 0
409.91 2.94  10
12 507.15
21.69
0
2852.20 2.02  10
11 3399.63
21.68
Table 4. Molar (H/C)utilized Calculated from the Numerical
Simulations
(H/C)converted (H/C)synthesized
pi = 4 MPa, L = 3 m, H2/CO = 2, pe = 0.1 MPa
2 2.1
pi = 4 MPa, L = 3 m, H2/CO = 1.5, pe = 0.1 MPa
2 2.09
latter part of the tube. The density decrease with the H2/CO feed
ratio is directly attributable to the decrease of the gas molecular
weight, with increasing H2/CO ratios.
Mass flow rates flowing down the packed tube are plotted in
Figure 3 for an inlet molar feed ratio of H2/CO = 2, inlet pressure
pi = 4 MPA, and reactor length L = 3 m. At the inlet of the packed
reactor tube the total mass flow rate entering consists of syngas
made up of H2 and CO alone. The fluid flowing downstream
consists of syngas (H2, CO, CO2, and H2O) along with paraffins,
CnH2nþ2, and olefins, CnH2n. There are also alkyl, CnFH2nFþ1, and
alkenyl, CnFH2nF
1, that propagate on the iron based catalyst. In
the study, paraffins and olefins with carbon atom numbers n < 20
are treated as gaseous, while those with n g 20 are considered
liquid. As the polymerization reactions are extended up to n = 30,
the alkyl and alkenyl propagating on the catalyst surface corre-
spond to C30H61 and C30H59, respectively. In Figure 3, at any
axial location, the difference between the syngas and total gas
represents the desorbed gaseous paraffins and olefins (n < 20),
while that between the total gas and total gas and liquid is an
account of the desorbed liquid paraffins and olefins (n g 20).
Finally, the difference between the total gas and liquid and the
total mass flowing in tube and propagating in catalyst represents
the amount of alkyl and alkenyl that propagate on the catalyst
surface. As shown in the figure, the total mass flow rate in the
packed tube consisting of the flowing mass (syngas, paraffins, and
olefins) and propagating mass (alkyl and alkenyl) remains
constant at the initial value verifying the overall conservation of
mass of species. As hydrogen and carbon monoxide adsorb to the
catalyst throughout the reactor length, the syngas is shown to
decrease continuously along the length of the tube. The adsorp-
tion of hydrogen and carbon monoxide is proportional to their
corresponding partial pressures, which in turn are directly related
to the total gas pressure and mole fractions. Thus, the highest
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 1. Axial variation of gas pressure.
Figure 2. Axial variation of gas density.
Figure 3. Axial variation of mass flow rate.
adsorption rates occur at the inlet of the tube, which coincide
with the largest decreases in the syngas flow rate. As can be seen
from the figure, for the first 0.5 m of the tube there is no
desorption of paraffins or olefins, and as such, the adsorbed mass
of H2 and CO on the catalyst is converted to the propagating
2248
ARTICLE
Figure 4. Axial variation of mass flow rate.
Figure 5. Axial variation of superficial gas velocity.
alkyl and alkenyl species. This suggests that the polymerization
reactions are characterized solely by chain propagation reactions
reaching higher carbon atom numbers with increasing axial
length. From this point on, paraffins and olefins start desorbing
from the catalyst and are added to the flow stream in the tube.
Around x = 0.8 m, the propagating alkyl and alkenyl rates reach a
maximum that corresponds to a minimum of the flowing stream
of mass (syngas, paraffins, and olefins). Beyond this point, the
sharp decrease of the propagating alkyl and alkenyl contributes to
the corresponding fast rate of increase in the desorbed paraffins
and olefins, causing the flowing mass stream in the tube to
increase, as shown in the figure. Thus, the second region starts
with chain termination reactions reaching higher carbon atom
numbers with increasing axial length (and thus desorption of
liquid species), resulting in limiting the extent of the chain
propagation reactions to lower carbon atom numbers. This in
turn starts limiting the termination reactions themselves to lower
carbon atom numbers. Around x = 1.9 m, the propagating alkyl
and alkenyl at n = 30 are depleted resulting in the flowing mass of
gas and liquid making up the total mass flow entering the reactor
tube. Beyond x = 1.9 m, desorption of liquid paraffin and olefins
ceases. This indicates that the end of the second region is marked
with the propagation reactions not reaching carbon number
atoms beyond n = 19. The constant liquid flow rate guarantees
a constant gas flow rate. This assures that the continuing
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 6. Variation of inlet superficial velocity with inlet pressure and
inlet feed ratio.
adsorption of H2 and CO, that occurs at decreasing rates, is
balanced out by desorption of low carbon number gaseous
paraffins and olefins. Thus, in the third region, where the chain
propagation reactions keep diminishing to lower carbon atom
numbers with increasing axial distance, the termination reactions
themselves decrease to lower carbon atom numbers.
Corresponding mass flow rates for inlet feed ratios of H2/CO =
1.5 and 1 are plotted in Figure 4. As can be seen from Figures 3 and
4, lower feed ratios result in higher mass flow rates, as lower H2/
CO mole fractions result in higher gas molecular weights, larger
densities, and thus larger mass flow rates. For the same inlet
pressure and packed tube length, the axial location where the
propagating alkyl and alkenyl species is a maximum (and the
flowing gas and liquid flow rate is a minimum) occurs around
x = 0.8 m for all three inlet feed ratios. The axial location, where
the propagating species are depleted and the desorption of liquid
paraffins and olefins ceases, decreases as the H2/CO feed ratio
increases, since the FT reaction rate increases with increasing
H2/CO feed ratio resulting in higher adsorption rates of H2 and
CO as attested from the decrease of syngas . It is for the same
reason that the amounts of gaseous and liquid paraffins and olefins
produced in the tube, as noted from Figures 3 and 4, decrease as
the feed ratio decreases.
The axial variation of the superficial gas velocity in the packed
tube is shown in Figure 5. The superficial gas velocity, as defined
from eq 52, is inversely proportional with pressure and gas
molecular weight and proportional to the total gas mass flow rate.
Initially, for a given feed ratio, the superficial gas velocity despite
the decrease in pressure goes through a slight minimum that
coincides with the minimum of the total gas mass flow rate shown
in Figures 3 and 4. Beyond that point, as the total gas mass flow
rate increases and then levels off while the pressure continues to
decrease, the superficial gas velocity is found to increase. Near the
latter part of the tube, the superficial gas velocity exhibits a sharp
increase that follows the sharp decrease of the pressure. The
increase of the superficial gas velocity with increasing initial H2/
CO feed ratio is due to the corresponding decrease in the gas
molecular weight. It is noted that the superficial gas velocity for a
fixed length reactor reflects the residence time of the gas, with
larger velocities corresponding to lower residence times, and thus
reaction times.
As explained earlier, the inlet superficial velocity is determined
in the computational model through a Newton
Raphson
2249
ARTICLE
Figure 7. Variation of inlet superficial velocity with reactor length and
inlet feed ratio.
iterative scheme that employs under-relaxation. Converged
values for the inlet superficial velocities as a function of inlet
pressure are plotted in Figure 6 for a tube length of 3 m and exit
pressure of 0.1 MPa. As expected from basic momentum con-
cepts, greater inlet pressures will result in greater superficial
velocities. The increase of the inlet superficial velocity with
increasing H2/CO feed ratio is again due to the decrease in
density with increasing H2/CO ratios.
Inlet superficial velocities as a function of the reactor length are
plotted in Figure 7 for an inlet pressure of 4 MPa. With the inlet
and exit pressures fixed, the momentum eq 44 dictates that higher
velocities are required in shorter reactors, verifying the decreas-
ing values of the inlet velocities with reactor length. Again, the
increase of the inlet superficial velocities with increasing H2/CO
feed ratios is due to the decrease in density with increasing feed
ratios.
Conversion performance relates to the overall consumption of
reactants rather than the formation of products. For reasons
discussed earlier, the rate of conversion is best expressed in terms
of the rate of carbon conversion, which is equal to the overall rate
of consumption of CO and CO2.
rate of carbon conversion ¼ ðN_ CO þ N_ CO2 Þinlet

ðN_ CO þ N_ CO2 Þexit ð60Þ
Conversion expressed in this way is not affected by CO2 being
produced or consumed. The calculated amount of carbon
consumed is directly equal to the amount of carbon in the FT
products. As discussed earlier with the FT reaction producing the
(CH2) monomer, the ratio of H/C is 2 regardless of the reactor
parameters. As a result, the rate of carbon conversion is exactly
the same as that for the total H2 conversion, defined as
rate of H2 conversion ¼ ðN_ H2 þ N_ H2 O Þinlet

ðN_ H2 þ N_ H2 O Þexit ð61Þ
The rate of total carbon conversion (or the rate of total H2
conversion) as a function of the syngas feed ratio is plotted for the
three inlet pressures in Figure 8 and for the four reactor lengths in
Figure 9. As illustrated in Figure 8, for a fixed reactor length, the
carbon conversion rate increases with both inlet pressure and
with H2/CO feed ratio. An increase in pressure, and hence partial
pressures, increases the adsorption and reaction rates, promoting
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 8. Variation of total carbon conversion rate with inlet feed ratio
and inlet pressure.
Figure 9. Variation of total carbon conversion rate with inlet feed ratio
and reactor length.
the rate of carbon consumption. An increase in the molar feed
ratio H2/CO results in an increase in the mole fraction of
hydrogen and a decrease in the mole fraction of carbon mon-
oxide. As can be seen from eq 25, an increase in the partial
pressure of H2 increases the FT reaction rate RFTS, while a
decrease in the partial pressure of CO tends to decrease it. With
the effect of the increase of pH2 dominating over the retarding
effect of the decrease of pCO, an increase in H2/CO results in an
increase of the carbon conversion rate. It is noted that total
carbon conversion rate is independent of the extent of the WGS
reaction, eq 4, since CO and CO2 are on opposite sides of the
equation.
The rate of total carbon conversion versus feed ratio for four
reactor lengths is plotted in Figure 9 for an inlet pressure of 4
MPa. The conversion rate is shown to increase with both reactor
length and feed ratio for a fixed inlet and outlet pressure. The
longer reactor lengths provide longer residence times (smaller
superficial velocities) for the carbon monoxide and hydrogen to
adsorb and react with the catalyst, thus increasing the carbon
conversion rate (see eqs 28
34). For a fixed reactor length, an
increase in the feed ratio again, as discussed in the above
paragraph, enhances the FT reaction rate resulting in an increase
in the carbon conversion rate.
2250
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Figure 10. Variation of fraction of total carbon conversion with inlet
feed ratio and inlet pressure.
Figure 11. Variation of fraction of total carbon conversion with inlet
feed ratio and reactor length.
The fraction of total carbon conversion defined as
ðN_ CO þ N_ CO2 Þinlet
ðN_ CO þ N_ CO2 Þexit
fraction of carbon conversion ¼
ðN_ CO þ N_ CO2 Þinlet
ð62Þ
is plotted versus the H2/CO feed ratio for the three pressures
with a reactor length of 3 m in Figure 10. The fraction of carbon
conversion increases with increasing feed ratio, but decreases
with increasing inlet pressure. The decrease of the fraction of
carbon conversion with inlet pressure is due to the increasing
carbon molar rates at the inlet of the reactor (denominator of
eq 62) that result from the corresponding increase of the
superficial inlet velocity with pressure, plotted in Figure 6, despite
the increase in the conversion rate (numerator of eq 62) with the
inlet pressure.
The fraction of carbon conversion versus the H2/CO feed
ratio for the four reactor lengths is plotted in Figure 11 for an
inlet pressure of 4 MPa. The fraction of carbon conversion is
shown to increase with feed ratio, as well as with increasing
reactor length. The increase of the fraction of carbon conversion
with increasing reactor length is due to both the increase in the
conversion rate illustrated in Figure 9 (numerator of eq 62), and
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 12. Variation of usage ratio with inlet feed ratio and inlet
pressure.
the decrease of the carbon flow rate at the inlet illustrated in
Figure 7 (denominator of eq 62) with decreasing inlet superficial
velocity. Despite the increase of the inlet superficial velocity (see
Figure 7) and thus the denominator of eq 62, the increase in the
FT reaction rate with the feed ratio results in the increase of the
fraction of carbon conversion with increasing H2/CO feed ratio,
as shown in Figure 11.
The usage ratio H2/CO is defined from
N_ H2in
N_ H2out
ðH2 =COÞusage ¼ ð63Þ
N_ COin
N_ COout
and is a measure of the ratio of the decrease of H2 to that of CO.
The production of synthesis gas is a major cost factor in the FT
process. Thus, as mentioned earlier, it is essential that as much of
the synthesis products (CO, H2, and CO2) are consumed to
provide useful products. One way to assess this is to compare the
usage ratio (eq 63) to the supplied inlet feed ratio. In Figure 12, at
a given supplied feed ratio, the usage ratio is shown to increase
with an increase in inlet pressure. An increase in total pressure
increases the partial pressures of H2 and CO, promoting
the adsorption of both and consequently their consumption. The
usage ratio thus increases since more H2 is consumed than CO as
dictated by eqs 1
4. As the supplied H2/CO feed ratio increases,
the mole fraction of H2 increases while that of CO decreases,
resulting in the increase of the usage ratio. For feed ratios H2/CO
of both 1 and 1.5, the usage ratio for all three pressures always
exceeds the feed ratio, indicating that (H2/CO)out < (H2/CO)in
and that there would be extra H2 entering the reactor. For these
two feed ratios, this mismatch is amplified with an increase in
pressure. Conversely, for the feed ratio of 2, the usage ratio is
found to be less than the feed ratio for all three pressures. This
would indicate that (H2/CO)out > (H2/CO)in and that there
would be extra CO entering the reactor. As can be seen, for each
inlet pressure, the usage ratio increases with the feed ratio. This is
because the carbon conversion rate increases with increasing feed
ratio, as illustrated in Figure 8, resulting in greater consumption
of hydrogen than carbon monoxide, and hence a greater usage
ratio. One can also see in Figure 12, that for an inlet pressure of 4,
a feed ratio of around 1.92 approximately matches the usage ratio.
Plots of H2/CO usage ratio versus H2/CO feed ratio for four
different reactor lengths at an inlet pressure of 4 MPa are shown
in Figure 13. As seen from the figure, for a given feed ratio and
inlet and exit pressures, a decrease in the reactor length increases
2251
ARTICLE
Figure 13. Variation of usage ratio with inlet feed ratio and reactor
length.
the usage ratio. This is due to the decrease in the carbon
conversion rate with decreasing reactor length, illustrated in
Figure 9. At a given reactor length and a fixed inlet pressure, an
increase in the feed ratio results in higher usage ratios. Again for
feed ratios of 1 and 1.5, the usage ratio exceeds the feed ratio,
resulting in (H2/CO)out < (H2/CO)in. The mismatch between
the two ratios decreases with an increase in reactor length,
resulting in higher carbon conversion rates and lower usage
ratios. Conversely, for the feed ratio of 2, the usage ratio is found
to be less than the feed ratio, indicating that (H2/CO)out > (H2/
CO)in. It can be seen that for a reactor length of 2 m, a feed ratio
around 1.936 approximately matches the usage ratio.
With the water
gas shift reaction of eq 4 being close to
equilibrium for iron catalysts considered in this study, the usage
ratio depends on the feed gas composition as the direction of the
WGS reaction depends on the feed ratio. By examining the FT
and WGS reactions, eqs 2 and 4, the usage ratio may vary from 2,
with no CO2 in the feed, to infinity, with no CO in the feed.
However, the case with no CO2 in the feed is likely to cause CO2
to be a product, as is the case in this study with the usage ratio
dropping below 2.
The product distribution of a Fischer
Tropsch process
depends on many reaction variables, the type of reactor, and
the catalyst used. The main products of the FT synthesis are R-
olefins and n-paraffins with some side oxygenate and branched
compounds. Mazzone and Fernandes3 varied the inlet superficial
gas velocity, inlet pressure, and H2/CO ratio independently,
while presenting their results. With the dependence of the
density and thus mass flow rate on inlet pressure, their choice
of independent variables is at best ambiguous. Also, for a given
inlet pressure and reactor length, a change in the entering H2/
CO ratio changes the inlet velocity and mass flow rate. In
addition, the exit pressure is a variable that was not reported.
In their model, the effects of the desorbed gaseous paraffins and
olefins mixing with the flowing synthesis gas, accounted for in
eqs 40
48, 52, and 53, were left out of the analysis. Also, no
information on the handling of the axial variation of the density,
superficial velocity, and gas molecular weight was reported.
The most direct way to assess the effects of the process
parameters on the FT product is to plot the carbon atom
selectivities as defined from eq 5. The change of the flow rate
entering the reactor with pressure, reactor length, and H2/CO
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 14. Variation of total selectivity of paraffins with inlet feed ratio
and inlet pressure.
Figure 15. Variation of total selectivity of paraffins with inlet feed ratio
and reactor length.
ratio is thus accounted for in the definition of the selectivities.
The total selectivities for all paraffins and olefins leaving the
reactor
30 30
Stotpar ¼ ∑ Sn
n¼1
par
Stotolef ¼ ∑ Sn
n¼2
olef
ð64Þ
are plotted in Figures 14
17, where the carbon atom selectivities
are estimated at z = L from eqs 55 and 56, respectively, for
paraffins and olefins. As the reaction rates of olefin desorption are
much greater than those for paraffins, the total olefin selectivities
are of the order of 0.82
0.86, whereas the corresponding
paraffin selectivities are in the range of 0.18
0.14. At a constant
syngas feed ratio, the total selectivity of paraffins is shown to
increase with either a decrease in inlet pressure (Figure 14) or an
increase with reactor length (Figure 15). This can be attributed
to the fact that either a decrease in the inlet pressure or an
increase in the reactor length reduces the gas velocities in the
reactor, as depicted by Figures 6 and 7, respectively. Reduced
reactor velocities increase gas residence times resulting in
enhanced fraction of total carbon (or hydrogen) conversion, as
illustrated in Figures 10 and 11. As paraffins are formed by the
addition of H to alkyls (see eq 8), an increase in adsorbed
2252
ARTICLE
Figure 16. Variation of total selectivity of olefins with inlet feed ratio
and inlet pressure.
Figure 17. Variation of total selectivity of olefins with inlet feed ratio
and reactor length.
hydrogen on catalyst surface promotes the rate of termination of
paraffins. In the alkyl mechanism, olefin formation occurs by
hydrogen abstraction (see eq 9); therefore an increase in the
adsorbed hydrogen on the catalyst would tend to decrease the
termination of the alkyls as olefins. In contrast, in the alkenyl
mechanism which predicts only the formation of olefins, olefin
termination occurs via hydrogen reduction, as seen from eq 12.
Thus, an increase in the hydrogen on the catalyst would tend to
increase olefin formation. With the alkyl mechanism dominating,
at a constant syngas feed ratio, the total olefin selectivity is found
to decrease with either decreasing inlet pressure (Figure 16) or
with increasing reactor length (Figure 17). These trends are
exactly reverse of those for paraffins depicted in Figures 14 and
15. This is because with negligible alkyl and alkenyl rates at the
exit of the reactor (see Table 3), at a given inlet pressure, reactor
length, and syngas feed ratio, the total selectivities of paraffins
and olefins add up to unity, as attested from eqs 55, 56, and 64.
An increase in the syngas feed ratio is shown to promote the
total selectivity of paraffins while stifling the total selectivity of
olefins. An increase in the H2/CO feed ratio results in the
increase of the H2 mole fraction (partial pressure) and decrease
in the CO mole fraction (partial pressure). As discussed earlier,
the increase in the H2/CO feed ratio augments the FT reaction
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 18. Variation of selectivity of paraffins with carbon number and
inlet feed ratio.
Figure 19. Variation of selectivity of olefins with carbon number and
inlet feed ratio.
rate (see eq 25) contributing to enhanced formation of the
monomer CH2 and, thus, an increase in total fraction of carbon
(and hydrogen) conversion as shown in Figures 10 and 11.
Again, the increase of hydrogen on catalyst, as discussed above,
promotes paraffin termination (see Figures 14 and 15), while
reducing olefin formation as illustrated in Figures 16 and 17.
The carbon atom selectivities of paraffins CnH2nþ2 and olefins
CnH2n, as given from eqs 55 and 56, respectively, are plotted in
Figures 18
23 as a function of carbon atom number for n =
1
30. It is noted again that desorbed hydrocarbons with a
carbon atom number of n = 20 or greater are considered to be
in the liquid state. As the rate of desorption of olefins is greater
than paraffins, the selectivity of olefins by far exceeds those of
paraffins with the exception of methyl (n = 1) and ethyl (n = 2)
group. The paraffin methane (CH4) is the only FT product
formed with n = 1 since methylene (CH2) acts as the monomer in
the synthesis reaction. With no olefin desorbed at n = 1, methane
has the highest rate of desorption than any other paraffin. For
n = 2, the low formation of the olefin ethylene (C2H4) is due to
the fact that ethylene is formed by the reaction of two methylene
species, rather than the termination of C2H5 or C2H3. As shown
in the figures, the selectivity of the paraffins beyond methane
initially dips at n = 2, then increases slightly, quickly going
through a peak at n = 3 or 4, and subsequently drops steadily with
2253
ARTICLE
increasing carbon atom number. For the olefins, after the low
selectivity of ethylene (n = 2), the selectivity of olefins increases
sharply, going through a maximum and then decreases steadily
with increasing atom numbers. These trends are consistent with
polymerization reactions, as noted in eq 15, where the probability
of formation of hydrocarbons decreases with increasing carbon
number.
Carbon atom selectivities for paraffins and olefins are plotted
in Figures 18 and 19, respectively, for an inlet pressure pi = 4
MPa, reactor length of L = 3 m, and three molar syngas feed
ratios. Paraffins are formed by the addition of H to alkyls (see
eq 8). As discussed earlier, an increase in the syngas feed ratio,
H2/CO, will naturally increase the mole fraction of H2, thus
increasing the rate of termination of paraffins. The significantly
larger paraffin termination rates at small carbon atom numbers
(n = 1, 2) that result with increasing feed ratio, diminish the
propagation of the alkyls resulting in the decrease of the carbon
selectivity for paraffins for n = 8 and beyond with increasing
H2/CO feed ratio, causing the crossover of the lines plotted in
Figure 18.
As documented earlier, an increase in the H2/CO ratio
diminishes the olefin formation via the alkyl mechanism, while
enhancing it via the alkenyl mechanism due to the increase of the
H2 mole fraction. Consequently, an increase in the syngas feed
ratio results in the decrease of olefin selectivities up to n = 11 due
to the steep increases in the low carbon number paraffins coupled
with the low selectivity of ethylene, and in the increase of olefin
selectivities beyond n = 11, demonstrated in Figure 19, compli-
menting the decreasing selectivity of paraffins at large carbon
atoms with H2/CO shown in Figure 18.
The carbon number selectivities of paraffins and olefins at
three different inlet pressures and for an inlet syngas feed ratio of
H2/CO = 2 and reactor length of L = 3 m, are plotted in
Figures 20 and 21, respectively. A decrease in the inlet pressure
while maintaining a constant H2/CO feed ratio, results in a
decrease in gas velocities, thus increasing the fraction of carbon
(hydrogen) conversion rates which favors the formation of
paraffins at the expense of olefin formation according to the
alkyl mechanism, while at the same time enhancing the olefin
formation as predicted by the alkenyl mechanism. As shown in
Figure 20, a decrease in the inlet pressure results in enhanced
paraffins selectivities at lower carbon number, followed by
crossover due to the diminishing propagation of alkyl species
Figure 20. Variation of selectivity of paraffins with carbon number and
inlet pressure.
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels
Figure 21. Variation of selectivity of olefins with carbon number and
inlet pressure.
with increasing carbon atom numbers. The crossover occurs at a
much higher carbon atom number and is hardly noticeable in the
figure due to the low selectivities of paraffins. The effect of the
inlet pressure is much more pronounced for the olefin selectiv-
ities depicted in Figure 21, where a decrease in the inlet pressure
increases the olefin selectivities for up to carbon atom number
n = 9. This is due to the increase of olefin formation via the
alkenyl mechanism that results from higher carbon and hydrogen
conversion rates with decreasing pressure (decreasing gas
velocities) that favor termination of growing chains and thus
promote the formation of light paraffin and olefin products.
Consequently, the propagating alkyl and alkenyl species increase
with increasing inlet pressure, promoting the formation of large
chain olefins and paraffins. Thus, as seen in Figure 21, for a
carbon number of n > 9 an increase in the inlet pressure is shown
to increase the olefin selectivities.
The effects of the reactor length on paraffin and olefin
selectivities are depicted in Figures 22 and 23, respectively.
The results are for an inlet pressure of 4 MPa, outlet pressure
of 0.1 MPa, and a syngas molar feed ratio of H2/CO = 2. As
discussed earlier, at a constant inlet pressure, an increase in the
reactor length increases residence time favoring the fraction of
carbon (hydrogen) conversion rate. This again favors the termi-
nation rates of light paraffins and olefins as discussed above,
Figure 22. Variation of selectivity of paraffins with carbon number and
reactor length.
2254
ARTICLE
Figure 23. Variation of selectivity of olefins with carbon number and
reactor length.
resulting in the increase of the selectivity of paraffins (for n e 9)
and olefins (for n e 7), as shown in Figures 22 and 23,
respectively. Higher termination rates at low carbon numbers
with increasing reactor lengths cause the propagating alkyl
and alkenyl species to decrease. This decrease results in the
crossover of the paraffin selectivities for n > 9 (Figure 22) and
olefin selectivities for n > 7 (Figure 23), where an increase in the
reactor length is found to diminish the paraffin and olefin
selectivities.
The carbon atom selectivities for several carbon atom range
fuel products are summarized in Table 5 as a function of inlet
syngas feed ratios, reactor inlet pressures, and lengths.
The mass flow rates for paraffins CnHnþ2, and olefins CnH2n,
leaving the reactor, as a function of the carbon number n, are
plotted in Figures 24
29. The mass flow rates are calculated by
multiplying the mole flow rates of paraffins and olefins, given
from eqs 57 and 58, respectively, with their corresponding
molecular weights given from eq 49.

 
2
m_ kpar ¼ Skpar N_ Cdesorbed MC þ 2 þ MH ð65Þ
k
m_ kolef ¼ Skolef N_ Cdesorbed ½MC þ 2MH  ð66Þ
As seen from the equations above, the variation of the mass
flow rates of paraffins and olefins with syngas molar feed ratio,
inlet reactor pressure, and reactor length directly follows
the trends of the carbon number selectivities discussed in
Figures 18
23 and that of the total carbon conversion rate
discussed in Figures 8 and 9.
As shown in Figures 24, 25, and 26, the mass flow rate of
methane is by far the largest among paraffins. There is a sharp
decrease in the production of ethane (n = 2) that goes through a
quick peak, then decreases gradually with increasing carbon atom
numbers. These trends are consistent with those for paraffin
selectivities discussed earlier. As seen from the three figures, at
low to moderate carbon atom numbers, the mass flow rate of
paraffins increase with increasing molar syngas feed ratio
(Figure 24), decreasing inlet pressure (Figure 25), and increasing
reactor length (Figure 26). These effects decrease with increasing
carbon atom number and completely diminish beyond n = 13
in Figure 24, n = 24 in Figure 25, and n = 13 in Figure 26.
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Energy & Fuels ARTICLE

Table 5. Calculated Selectivities of Conventional Fuels (TR = 270 °C, pe = 0.1 MPa, O = 0.6)
H2/CO total paraffins total olefins SNG LPG light petroleum heavy petroleum petroleum kerosene diesel middle distillates softwax
carbon number 1
30 1
30 1
2 3
4 5
7 8
10 5
10 11
12 13
20 11
20 21
30

pi = 4 MPa 1 0.251 0.749 0.147 0.319 0.253 0.127 0.380 0.050 0.083 0.132 0.021
L=3m 1.5 0.287 0.713 0.176 0.288 0.238 0.126 0.364 0.051 0.092 0.143 0.028
2 0.318 0.682 0.203 0.272 0.227 0.122 0.348 0.051 0.095 0.145 0.032
pi = 3.5 MPa 1 0.250 0.750 0.148 0.344 0.257 0.121 0.378 0.045 0.070 0.114 0.016
L=3m 1.5 0.288 0.712 0.179 0.311 0.243 0.121 0.363 0.047 0.079 0.126 0.021
2 0.319 0.681 0.206 0.292 0.231 0.118 0.348 0.047 0.082 0.129 0.024
pi = 3 MPa 1 0.250 0.750 0.150 0.375 0.258 0.112 0.370 0.039 0.056 0.095 0.010
L=3m 1.5 0.289 0.711 0.182 0.338 0.245 0.114 0.359 0.042 0.065 0.107 0.015
2 0.322 0.678 0.211 0.316 0.234 0.111 0.345 0.042 0.068 0.111 0.017
pi = 4 MPa 1 0.228 0.772 0.127 0.304 0.259 0.137 0.395 0.055 0.093 0.148 0.025
L=2m 1.5 0.252 0.748 0.145 0.276 0.245 0.137 0.382 0.057 0.106 0.163 0.034
2 0.272 0.728 0.161 0.262 0.236 0.134 0.371 0.058 0.111 0.168 0.038
pi = 4 MPa 1 0.240 0.760 0.138 0.313 0.256 0.131 0.388 0.052 0.087 0.139 0.023
L = 2.5 m 1.5 0.271 0.729 0.161 0.283 0.242 0.131 0.373 0.054 0.098 0.152 0.031
2 0.296 0.704 0.183 0.268 0.232 0.128 0.360 0.054 0.102 0.155 0.035
pi = 4 MPa 1 0.251 0.749 0.147 0.319 0.253 0.127 0.380 0.050 0.083 0.132 0.021
L=3m 1.5 0.287 0.713 0.176 0.288 0.238 0.126 0.364 0.051 0.092 0.143 0.028
2 0.318 0.682 0.203 0.272 0.227 0.122 0.348 0.051 0.095 0.145 0.032
pi = 4 MPa 1 0.259 0.741 0.155 0.324 0.250 0.124 0.374 0.048 0.079 0.127 0.020
L = 3.5 m 1.5 0.302 0.698 0.190 0.292 0.234 0.121 0.355 0.049 0.087 0.136 0.027
2 0.338 0.662 0.222 0.273 0.221 0.116 0.337 0.048 0.089 0.137 0.030

Figure 24. Variation of mass flow rate of paraffins with carbon number Figure 25. Variation of mass flow rate of paraffins with carbon number
and inlet feed ratio. and inlet pressure.

mass flow rate of olefins decreases with increasing molar syngas

The absence of any crossover in these graphs, in contrast with
those that were encountered in the selectivity plots, is due to the
increase in the carbon conversion rate with increasing syngas feed
ratio, increasing inlet pressure, and increasing reactor length, as
depicted in Figures 8 and 9.
Corresponding mass flow rates of olefins are plotted in
Figures 27
29. As can be seen, ethylene has the lowest mass
flow rates of olefins, and it is not affected by the variation of
syngas feed ratio, inlet pressure, or reactor length. Beyond
ethylene, the olefin mass flow rates are shown to go through a
quick maximum around n = 4 (butanele) and, then, gradually
decrease with increasing carbon atom number. In Figure 27, the
2255
feed ratio for n e 5, while it is shown to increase for n g 6 with
increasing H2/CO. This is again due to the increase of the H2
mole fraction with increasing H2/CO that retards the olefin
termination by the alkyl mechanism at low carbon atoms, while
enhancing olefin formation via the alkenyl mechanism. In
Figure 28, the olefin mass flow rates are shown to increase
with increasing inlet pressure. As can be seen from Figure 27
and 28, the inlet syngas feed ratio and inlet pressure, respectively,
are found to significantly affect the olefin mass flow rates at large
carbon atom numbers. In Figure 29, the mass flow rate of olefins
is shown to increase with increasing reactor length. These
effects are the largest at n = 3 (propylene), and decrease with
dx.doi.org/10.1021/ef200160x |Energy Fuels 2011, 25, 2242–2257
Energy & Fuels ARTICLE

Figure 26. Variation of mass flow rate of paraffins with carbon number Figure 29. Variation of mass flow rate of olefins with carbon number
and reactor length. and reactor length.

Figure 27. Variation of mass flow rate of olefins with carbon number
and inlet feed ratio.
Figure 28. Variation of mass flow rate of olefins with carbon number
and inlet pressure.
increasing carbon atom number until they completely diminish
beyond n = 16.
2256
’ CONCLUSIONS
The effects of reactor length, inlet pressure, and syngas feed
ratio on paraffin and olefin selectivities and mass flow rates in a
Fischer
Tropsch synthesis have been documented. The carbon
conversion rate is found to increase with inlet pressure, reactor
length, and syngas molar feed ratio, while the usage ratio is shown
to increase with inlet pressure and molar feed ratio and to
decrease with increasing reactor length.
The total selectivity of paraffins is shown to increase with
increasing syngas feed ratio and reactor length and to decrease
with increasing inlet pressure. On the other hand, the total
selectivity of olefins is found to decrease with increasing syngas
feed ratio and reactor length, while increasing with increasing
inlet pressure.
At low to moderate carbon atom numbers, the mass flow
rate of paraffins increase with increasing syngas feed ratio,
decreasing inlet pressure, and increasing reactor length. These
effects subside with increasing carbon number. The mass flow
rate of methane is by far the greatest among paraffins. Mass
flow rates of olefins exceed corresponding paraffin rates except
for n = 2, where the mass flow rate of ethylene is the lowest of
olefins. The mass flow rates of olefins decrease with increasing
syngas feed ratio at low carbon atom numbers, but increase with
the feed ratio at large carbon atom numbers. Olefin mass flow rates
are shown to increase with increasing inlet pressure and reactor
length.
Finally, three distinct stages of the polymerization reactions
are identified. At the initial stage, all of the adsorbed syngas is
converted to propagating alkyl and alkenyl species with increas-
ing carbon atom numbers, as chain termination reactions do
not occur at this stage. The second stage is characterized with
desorption of olefins and paraffins, as chain termination reac-
tions become significant, decreasing the propagation reaction
rates to lower carbon numbers. Eventually, the decreasing
propagation reactions at lower carbon numbers in turn limit
the termination reactions to lower carbon numbers themselves.
The second stage ends with the ceasing of desorption of liquid
olefin and paraffins. At the last stage, the absence of desorbed
liquids results in constant gas flow rates, as any decrease in
syngas results in the formation of low carbon number gaseous
olefins and paraffins.
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Energy & Fuels ARTICLE

’ AUTHOR INFORMATION
Corresponding Author
*E-mail: alex.moutsoglou@sdstate.edu.

’ ACKNOWLEDGMENT
This work has been supported through funds provided by
the Department of Transportation under grant DTOS59-07-G-
00054 and Department of Defense under grant W911NF-09-
2-0024.

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