Paper 6

International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)
Volume No.2, Issue No.1, pp : 31-39 1 Jan. 2013

IJSET@2013 Page 31

An Optimization Study of FischerTropsch Synthesis Using Commercial
Cobalt Catalyst
Hanif A. Choudhury, Vijayanand S. Moholkar

Center for Energy, Indian Institute of Technology Guwahati, Guwahati, Assam, India
vmoholkar@iitg.ac.in

ABSTRACT
Fischer-Tropsch synthesis with a commercial cobalt
catalyst (Albemarle) has been carried out under various
combinations of two process parameters, viz. reaction
pressure and GHSV (gas hourly space velocity) using
synthesis gas with molar ratio of H
2
/CO =2. The optimum
set of reaction parameters that yielded hydrocarbon
product in the desired carbon number range of C
10
-C
14
and
chain growth probability factor of 0.62 was: pressure =3
MPa, GHSV =3600 h
-1
and temp =493 K. I n the pressure
range of 1-2 MPa at lower GHSV of 1800 h
-1
, products
obtained were in the carbon number range of C
14
-C
24
. An
analysis of the link between operating parameters and
product distribution has also been given using alkyl
mechanism of FT synthesis and Blyholder model for
adsorption of CO on metal sites.
Key words: Fischer-Tropsch synthesis, cobalt catalyst,
Alkyl mechanism, GHSV
1. Introduction
FischerTropsch synthesis (FTS) is a well known
process for production hydrocarbons from synthesis gas
derived from different sources such as coal gasification,
natural gas reforming, biomass gasification [1]. Recently,
the interest of scientific and industrial community in
FischerTropsch (FT) synthesis has been renewed due to
fast depletion of fossil fuels, fluctuating prices of crude oil
and concerns of global warming due to greenhouse gas
emission. Last decade has seen immense research activity
worldwide in development of as well as implantation of
various renewable energy technologies, such as solar, wind,
and biofuels. Despite these efforts only a small fraction of
total energy demand is met through renewable sources. As
per the report of US Department of Energy (DoE), a
cumulative contribution of solar, wind and biofuels is 1.5%
of the energy consumption of USA [2]. The major energy
needs of our society are in terms of electricity and
transportation fuel. The FT synthesis tries to fulfill the
latter need due to its ability of manufacturing synthetic
diesel and gasoline through renewable energy sources such
as biomass gasification. FT technology also gives
opportunity to utilize remote and inaccessible energy
sources such as reserves of natural gas by setting local
plants for conversion of natural gas to synthesis gas and
further liquefaction of this gas to diesel and gasoline.
Similarly, gasification facilities can also be set up near
remote or deep coal deposits with further liquefaction of this
gas to transportation fuels through FT technology [3].
FT synthesis is essentially a catalytic reaction. The
active and selective catalysts for the FT reaction are mainly
based on cobalt or iron. Cobaltbased catalysts are very
popular since they are promising for longchain
hydrocarbon synthesis [4-5]. Supported cobalt catalysts have
been extensively studied for FischerTropsch synthesis
(FTS) because of their higher activity compared to iron
catalysts [56]. The FT synthesis process involves
simultaneous large number of reactions and the product
spectrum consisting of a complex multi component mixture
of linear and branched hydrocarbons and oxygenated
products. Thus, the selectivity of the products (and not mere
the extent yield or conversion) is a crucial facet of an
efficient and viable FT technology. Main products of the FT
synthesis are linear paraffins and olefins. The general
reactions of FTS are summarized as follows:
Paraffins:
2 2 2 2
(2 1)H CO C H H O
n n
n n n
+
+ + + (R.1)
Olefins:
2 2 2
2 H CO C H H O
n n
n n n + + (R.2)
Water gas shift reaction:
2 2 2
CO H O CO H
+ +
(R.3)
Oxygenates:
2nH
2
+ nCO C
n
H
2n
O + (n-1) H
2
O (R.4)
Type, composition and nature of catalyst govern
the selectivity of products from FT process, and hence,
proper selection of catalyst as well as optimization of the
process conditions is of vital importance in FT process.
The carbon number of the product hydrocarbon
(either chain or branched hydrocarbon) is determined by the
process conditions, viz. temperature, pressure and space
velocity. Increase in temperature results in shifts towards the
product with lower carbon number. Several previous authors
have described the effect of these parameters on the yield
and selectivity of the FT process. Dictor and Bel [7],
Donnelly and Scatterfield [8], Mirzaei et al. [9] and
Anderson [10] have studied the effect of temperature on FT

IJSET@2013 Page 32

synthesis. They observed an increase of olefin to paraffin
ratio with increasing temperature for potassium promoted
precipitated iron catalyst. Effect of total pressure on the
product selectivity on alkaline promoted iron catalyst has
been reported by Dry [11]. Donnelly and Scatterfield [8]
found that increasing the H
2
/CO ratio in the reactor feed
results in production of lighter hydrocarbon (with lower
carbon number). The influence of the space velocity (or in
other words, residence time) of the synthesis gas on the
selectivity has been investigated by Bukur et al. [12].
Kuipers et al. [13] have investigated increase in the olefin to
paraffin ratio with increasing space velocity (and hence,
resulting in decrease of the conversion due to smaller
residence time) on a polycrystalline cobalt foil. Similar
studies have also been done by Bukur et al. [12] on a
commercial (Ruhrchemie) supported iron catalyst
(Fe/Cu/K/SiO
2
), and Iglesia et al. [14] on TiO
2
supported
ruthenium catalysts. Bukur et al. [12] have reported no
effect of the space velocity on the molecular weight (i.e. the
carbon number) of the hydrocarbons, while Iglesia et al. [14]
have observed an increase in the average molecular weight
of the products with decrease of the space velocity. The
selectivity to methane and olefins has been reported to
reduce with decreasing space velocity, while the selectivity
towards paraffins remains unchanged.
In this study, we have attempted to optimize the FT
process using commercial cobalt catalyst procured from
Albemarle, Netherlands using a fixed bed reactor. The
optimization variables are pressure and space velocity. The
temperature of the process has been kept constant, as the
effect of temperature on product distribution is well known
[15], in that higher temperatures favor smaller carbon
number hydrocarbons. The physical cause leading to this
effect is higher desorption of tendency of the reactants from
catalyst surface at elevated temperature. This optimization
study will give insight into the variation in product
selectivity in terms of carbon number with optimization
parameters using stoichiometric synthesis gas with ratio of
H
2
to CO as 2:1. Such a study is also important for the best
and effective use of the cobalt catalyst, taking into
consideration high cost of cobalt.

2. Experimental
2.1. Catalyst
The cobalt based catalyst was procured from M/s
Albemarle, Netherlands. The exact composition of the
catalyst was not undisclosed to us under the terms and
conditions of an agreement between Albemarle and the
Indian Institute of Technology Guwahati. However, BET
and TPR study of the catalyst was done in order to
understand the surface and reduction property of the
catalyst, which is a prerequisite for any heterogeneous
catalyst.
2.2 Catalyst characterization
Temperature programmed reduction (TPR) was
performed using Micromeritics TPD/TPR 2720 system to
determine reducibility of cobalt catalyst. The catalyst (0.3 g)
was reduced in a flow of 5% H
2
/Ar (30 cm
3
/min) with a
ramp rate of 10
o
C/min to 1073 K. A thermal conductivity
detector (TCD) was used to measure H
2
consumption. The
detector output was calibrated based upon 100% reducibility
of Ag
2
O powder, and a H
2
O trap was used to remove H
2
O
produced during the reduction. The degree of reduction of
the catalyst was calculated by using data of TPR
measurements as follows [16]:
2
2
H consumption below 723 K
% reduction = 100
Total H consumption in TPR experiment

(1)
2.3 Experimental setup and protocol
Experimental Setup: A schematic diagram of the reactor
and its accessories is shown in Figure 1. A xed bed tubular
reactor (MOC: SS 316, thickness: 2 mm, ID: 6.35 mm or
in.) was used for all reactions. The reactor had two gas
supply lines of 6.35 mm ( in.) ID, each for purge gas
(nitrogen) and synthesis gas (mixture of CO and H
2
). The
synthesis gas supply line was wrapped with thermal tapes so
as to preheat the feed gas to 423 K. The reactor effluent line
(ID 6.35 mm) was also heated in a similar manner to 373 K
to avoid any condensation of the product in the line prior to
backpressure regulator valve. Thereafter, no thermal
wrapping was given to the product lines, thus maintaining
the temperature in them at ambient condition, where higher
hydrocarbon products can condense. The liquid product was
collected in a trap (gasliquid separator) kept at ambient
temperature. Cold water (at 298 K) was circulated in a
jacket around the trap so as to achieve maximum possible
condensation of the hydrocarbon products. The lighter
hydrocarbons and unreacted reactant gases are removed
from the trap and purged through a gas flow meter. The ow
rate of feed synthesis gas was controlled using mass flow
controller (Make: Eureka Ml Flow, Range: 0500 cm
3
/min).
Catalyst (1 g) was placed inside the reactor enclosed
between glass wool plugs. The catalyst was reduced in situ
at 673 K for 12 h under a stream of 50% H
2
and N
2
mixture
(0.1 MPa pressure, 15 ml/min). After 12 h of reduction, the
temperature was reduced to 473 K under the constant flow
of hydrogen. Synthesis gas was introduced at a particular
space velocity (GHSV), and pressure was gradually
increased and set at the desired value. The temperature
inside the reactor was monitored using two thermocouples,
one at the catalyst bed and other at the surface of reactor.
These temperatures were maintained constant by circulating

IJSET@2013 Page 33

cooling water through a thermal jacket (in the form of in.
copper tubing) wrapped around the reactor. Experiments
were performed for five different combinations of reaction
pressure and GHSV. The conditions for each of the five
experiments are listed in Table 1 and designated as protocols
1 to 5.
Materials: All gases used were procured from M/s Vadilal
Gas Ltd. (Gujarat, India, purity: 99.999%). The gas
cylinders containing reaction mixture (H
2
/CO = 67%/33%
v/v) were connected to gas supply lines through twostage
high pressure regulator. The analyses of the gaseous
products in the reactor effluent were performed by an online
gas chromatograph (Make: Thermo Fischer Ceres 800 Plus
system) using PorapackQ column provided with a thermal
conductivity detector (TCD). The liquids products were also
analyzed by the same GC provided with a flame ionization
detector (FID) using BP10.5 column. For characterization
of gas chromatograph, hydrocarbon standards in the carbon
number range of C5-C24 were procured from Sigma-
Aldrich.
Analysis:
1. The CO conversion (%) has been calculated
according to the following equation:
( ) ( )
( )
CO conversion = 100
CO CO
in out
CO
in
n n
n

(2)
2. The molar selectivity toward the individual
components on carbon basis has been calculated according
to the equation:
1
i
i n
i
j
y
m
y
=
=

(3)
y
i
= mole fraction of component i in reactor effluent

3. Results and Discussion
3.1 The reduction profile and the surface properties
of the catalyst
TPR profile of the cobalt oxide catalyst is depicted
in Figure 2. It can be observed that the reduction process of
the catalyst occurs in two distinct stages. The first peak near
573

K is ascribed to the transformation of Co
3
O
4
to CoO,
whereas the second peak near 743

K represents the
transformation of CoO to Co [17,18]. The proposed scheme
for the reduction of cobalt oxides might be written as
follows:
2
H
3 4 2
Co O 3 CoO + H O
(first stage at
573 K) (R.5)
2
3H
2
3 CoO 3 CO + 2 H O
(second stage between 720 and 770 K) (R.6)
Based on calculations according to equation 1, the
reducibility the cobalt catalyst was found to be 33%. For
BET (BrunauerEmmettTeller) surface area determination
of the catalyst, 0.3 g catalyst sample was degassed at 423 K
for 2 h, and then heated at 10 K/min to 423 K and held for 2
h before analysis. The BET surface area of the catalyst was
determined as 190 m
2
/g by N
2
physisorption at 77 K (Make:
Beckcoulter). Despite having large surface area, the lower
reducibility of the catalyst could be due to difficulty in the
reduction of CoO to Co.
3.2 Effect of operation conditions on product profile
To identify and optimize the process condition of
FischerTropsch reaction, effects of pressure and the gas
flow rate (GHSV) on selectivity of the products were
investigated. The results of reactions conducted at different
conditions were adjudged and compared with yardsticks of
overall CO conversion and selectivity for hydrocarbons in
the desired carbon number range.
Effect of total reaction pressure: FTS reaction is essentially
a polymerization type reaction, in which the CH
2
units
formed from adsorbed CO and H
2
reactant gases add up to
form hydrocarbons of different chain length. Thus, as
evident from reactions R.1, the numbers of product moles in
FTS reaction are less than reactant moles resulting in
positive pressuredependence, as per Le Chateliers
principle. An obvious consequence of these effects is that
increase of reaction pressure also promotes the FTS
reaction, leading to an increase in the CO conversion. With
increasing pressure, longer chain hydrocarbons are likely to
form that could possibly condense and saturate the catalyst
pores by liquid product. To assess effect of reaction pressure
on product selectivity, we have carried out a series of
reactions at reaction pressure range of 1 to 3 MPa using
synthesis gas with molar ratio of H
2
/CO as 2:1 and
temperature of 493 10 K. At each reaction pressure, the
reduced catalyst was tested for 10 h. The results are
presented in the Fig. 3 for reaction pressures of 1, 1.5 and 2
MPa, respectively, at GHSV of 1800 h
1
. It is clearly
observed that with the increase in the total pressure, there is
an increase in the carbon number of the product, i.e. longer
chain hydrocarbons that condense at ambient temperature.
This also shows increasing trend in liquefaction of synthesis
gas with rising reaction pressure. At a reaction pressure of 1
MPa, the product molar selectivity is toward C
12
. An
increase in the pressure to 1.5 MPa shifts the product molar
selectivity towards the longer hydrocarbons (in the range
C
16
C
18
), which is evident from the product profiles
depicted in Fig. 3. Further increase in the pressure to 2 MPa

IJSET@2013 Page 34

shows interesting trend in that highest selectivity is seen for
C
24
with moderate selectivities in the range of C
14
C
16
;
while selectivity in the intermediate carbon number range of
C
18
C
22
is, however, lower than both C
14
C
16
and C
24
. At
constant GHSV of 1800 h
1
, the rise in reaction pressure
from 1 to 2 MPa increased CO conversion by approximately
30%.
An explanation for the observed results can be
given as follows: As per the alkyl mechanism Figure 4, the
FT reaction is essentially a chain polymerization type
reaction which is initiated by chemisorption of the carbon
monoxide on the catalyst surface. The carbon monoxide is
believed to have dissociative adsorption on the catalyst
surface. Adsorption of carbon monoxide on the cobalt
catalyst surface has been reported to be on the ontop site of
Co(0001) [19], which is mainly due to interaction between
filled 5orbital and the double degenerated 2 orbital
[20] and the center of the metal dband as shown in Figure
5. Charge is donated from carbon to the metal by the 5
bond and stabilized by back-donation from the metal d-
orbitals to the 2* antibonding molecular orbitals,
weakening the CO bond. Dissociation of chemisorbed CO
results in formation of surface carbon and surface oxygen.
The surface oxygen is removed either by adsorbed hydrogen
(with formation of water) or adsorbed CO (with formation
of CO
2
) [21]. The surface carbon, on the other hand, can
undergo sequential hydrogenation to yield intermediate
methylidyne (CH), methylene (CH
2
) and methyl (CH
3
)
species. In the overall FTS reaction, the CH
3
surface species
plays role of initiator, while CH
2
surface species plays role
of monomer. These species react (either by |hydrogen
abstraction or hydrogen addition) to form long chain
hydrocarbon products, either oolefin or nparaffins. A
higher pressure causes greater adsorption of carbon
monoxide on the catalyst surface, causing greater formation
of surface species (CH, CH
2
and CH
3
), and greater extent of
reaction among them to form hydrocarbon product with
higher carbon number (or a longer chain hydrocarbon).
Hence with increase in the pressure the product selectivity
increases towards the longer hydrocarbons.
Effect of synthesis gas flow rate: Gas flow rate in the
reactions has been measured in terms of the gas hour space
velocity (GHSV). The GHSV influences the residence time
of the gas with the catalyst. To understand the possible
effect of GHSV on the selectivity of the products in terms of
carbon number, we have done experiments at 7 different
GHSVs, viz. 24000, 19200, 14400, 9600, 4800, 3600 and
1800 h
1
. In the GHSV range of 24000 h
1
to 4800 h
1
, no
liquid hydrocarbon products were obtained. This essentially
means that no FTS reaction occurred for these gas hour
space velocities. Even if any FTS reaction occurred, the
yields of gaseous products would have been in too low
concentrations to be detected by the gas chromatograph.
Further reduction of GHSV in the range of 36001800 h
1
,

significant fraction of liquid hydrocarbons (C
5+
) were
observed in the product. The effect of GHSV on the
selectivity of products can be deduced from product profile
depicted in Fig. 3. It could be inferred that an increase in
reaction pressure from 2 to 3 MPa at a constant GHSV of
3600 h
1
, the carbon number range of the product increases
from C
6
C
10
to C
10
C
14
. Similarly, at a constant pressure of
2 MPa, reduction in the GHSV from 3600 to 1800 h
1

results in significant rise in the carbon number of product
from C
6
C
10
to C
14
C
24
. These results show that the product
distribution of the FT reaction in terms of carbon number is
dominated by combined effect of reaction pressure and
GHSV.
An explanation to these results can be given as
follows: With higher residence time, there is longer
interaction between catalyst particles and the gas molecules
leading to higher adsorption of the reactant molecules. This
phenomenon also leads to prolongation of the residence time
of reactants and reaction intermediates on the catalyst
surface causing further hydrogenation and oligomerization
of shortchain hydrocarbons resulting in long chain products
(C
5+
) that condense at ambient conditions. Similar
observations have been made in previous studies by Dictor
and Bell [7], Donnely and Satterfield [8], Bukur et al. [12],
Kuipers et al. [13] and Wang et al. [22] have also reported
decrease in the olefin to paraffin ratio of the product with
decreasing space velocity, indicating readsorption of
olefins and further hydrogenation to paraffins.
4. Conclusion
Present study using commercial cobalt catalyst has
attempted to optimize two important process parameters of
FT synthesis, viz. the total reaction pressure and the
residence time. Interesting trends in the product profile of
the FTS reaction were observed from a set of experiments
with permutation-combination of above-mentioned
parameters. Main goal of our experiments was to deduce the
influence of GHSV and reaction pressure on product profile,
and optimize the reaction conditions for products with
carbon number C
12
or higher, which is the typical range of
hydrocarbons in diesel. Among the range of reaction
pressures and GHSV attempted in this work, reaction
pressure range of 12 MPa with GHSV 1800 h
1
as in
protocol 1, 2 and 3 gives maximum selectivity towards C
14
C
24
. Moving towards a higher reaction pressure of 3 MPa,
with a faster GHSV of 3600 h
-1
or higher as in protocol 5,
the products selectivity shifts in the desired range C
10
C
14

although CO conversion is to some extent lesser than

IJSET@2013 Page 35

protocols 1, 2 and 3. Thus, the optimum set of parameters
for the FT process with commercial catalyst used in this
work is found to be pressure of 3 MPa and GHSV of 3600 h
-
1
. We believe that these results will be useful for design and
optimization of a large scale FT using the same catalyst.

Acknowledgement
This research was supported by Ministry of New and
Renewable Energy, Government of India under grant no.
19/20/2007-R&D/BE dated 06.08.2008.

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Table 1: FTS reaction data at different Pressure and GHSV
Protocol Pressure
(MPa)
CO Conversion % GHSV(h
1
) Molar
Selectivity
Protocol 1 1 28 1800 C
12
C
16

Protocol 2 1.5 34 1800 C
16
C
20

14
C
24

6
C
10

10
C
14

Figure 1: Experimental setup

IJSET@2013 Page 38

100 200 300 400 500 600 700 800
0.00
0.02
0.04
0.06
0.08
0.10
I
n
t
e
n
s
i
t
y

i
n

a
.
u
.
Temperature (
0
C)

Figure 2: TPR profile of Cobalt catalyst

Figure 3. Product profile and distribution in different experimental protocols

IJSET@2013 Page 39

CO
C
+2H
-H
2
O
+H
CH
CH
2 +H
Initiation:
Monomer
Surface
Carbon
Surface
methylidene
R CH
2 CH
2
R
Chain initiator
CH
2
CH
3
R
Propagation:
Termination/desorption
CH
3
+H
H
2
C CHR
H
3
C CH
2
R
HOH
2
C CH
2
R
o-olefine
n-paraffin
n-alcohol
Surface
methylene
'Alkyl' mechanism

Figure 4. Alkyl mechanism

M
C
O
Valence d-orbitals
2 * t
5o

Figure 5. Molecular orbital diagram of CO to a metal site according to the Blyholder model. (redrawn with modifcations from ref.
[24]).

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International Journal of Scientific Engineering and Technology (ISSN : 2277-1581)

Volume No.2, Issue No.1, pp : 31-39 1 Jan. 2013

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