Journal of Environmental Chemical Engineering 5 (2017) 54–62

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Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

Effect of CO2 co-feeding on the conversion of syngas derived from waste

to liquid fuel over a bi-functional Co/H-ZSM-5 catalyst
Michael Olawale Daramola* , Khuthadzo Matamela, Olawumi Oluwafolakemi Sadare
School of Chemical and Metallurgical Engineering, Faculty of Engineering and The Built Environment, University of the Witwatersrand, Private Bag X3, Wits
2050, Johannesburg, South Africa

A R T I C L E I N F O A B S T R A C T

Article history:
Received 25 July 2016 A bi-functional Co-HZSM-5 catalyst was synthesised by the Incipient Wetness Impregnation (IWI) of
Received in revised form 16 November 2016 cobalt onto H-ZSM-5 and effect of CO2-co-feeding on the performance of the catalyst during Fischer
Accepted 17 November 2016 Tropsch (F-T) was investigated. Physico-chemical property of the catalyst was checked with N2
Available online 18 November 2016 physisorption (for BET surface area), Transmission Electron Microscopy and Scanning Electron
Microscopy equipped with EDS. Effect of CO2 co-feeding was investigated at Gas Hourly Space Velocity
Keywords: (GHSV):1200 ml h
1 g
1; pressure: 15 bar, temperature: 250  C; and H2/CO ratio: 2.5; with a syngas
Bi-functional catalyst mixture containing 5% CO2. Pre-calibrated GCs were used to analyse the reaction products. The BET
Syngas
surface area, the pore volume and the pore size of the catalyst were 292 m2/g, 0.18 cm3/g and 2.83 nm,
CO2 co-feeding
respectively. TEM images showed that cobalt particles were well dispersed within the support. In the
Fisher-Tropsch
Gas-to-liquid presence of CO2 co-feeding, CO conversion was 73% and CO conversion was 53% without CO2 co-feeding.
Cobalt catalyst In addition, the co-fed CO2 was converted to hydrocarbons and a CO2 conversion of 63% was obtained. The
selectivity of the catalyst to methane was 53%, 34% to C2, <4% to C4-C5 and <10% to C6+ in the presence of
CO2 co-feeding. Co-feeding CO2 also affected the selectivity of the catalyst to olefin as well. Selectivity of
the catalyst to C3 decreased from 43% to 35% while C4 increased from 25% to 32% during CO2 co-feeding.
However, selectivity of the catalyst to C6+ olefin hydrocarbon increased from 9% to 15% during CO2 co-
feeding.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction Gasoline (MTG) synthesis, and (iv) Methanol-to-Olefins (MTO)

Management of waste has been a crucial and delegated
responsibility, undertaken on behalf of the industry, public
authorities by waste management specialists. Waste accumulation
has been known to create various problems to the environment
and to the human health. These problems are aggravated when
waste accumulates at incorrect landsite [1]. However to solve
environmental problems and ensure a healthy living, waste
management is very essential. Therefore the need for environ-
mentally acceptable waste disposal methods and/or beneficiation
has become a priority in developing countries like South Africa.
One way to beneficiate solid waste materials is to gasify them to
syngas (major components are CO and H2). Syngas gas can be used
to produce a variety of chemicals and liquid fuels. Liquid fuels can
be made from syngas via four basic processes: (i) Higher alcohol
synthesis, (ii) Fischer-Tropsch (F-T) synthesis, (iii) Methanol-to-
* Corresponding author.
E-mail address: michael.daramola@wits.ac.za (M.O. Daramola).
synthesis [2]. Higher alcohol synthesis focuses on ethanol
production, and has enjoyed much attention, but still offers a
low productivity and poor selectivity. Fischer-Tropsch synthesis is
a surface-catalyzed polymerization reaction that involves conver-
sion of synthesis gas (CO and H2) derived from coal, natural gas,
heavy oil or biomass into hydrocarbons consisting of paraffins,
olefins, alcohols and aldehydes Fischer-Tropsch (F-T) synthesis
produces a wide range of mainly linear paraffinic hydrocarbons,
and the product distribution depends on the type of catalyst, the
process conditions and reactor configuration [2]. After F-T reaction,
the obtained long-chain linear paraffins are cracked further into
short-chain hydrocarbons in fluidized-bed catalytic cracking (FCC)
units to maximize the realization of the desired product fractions
[3]. Cobalt (Co) and Iron (Fe) are the two most metal catalysts
employed in the commercial F-T synthesis [4,5]. These metal
catalysts can catalyze F-T synthesis at temperatures below 523 K,
also known as the Low-Temperature Fischer-Tropsch (LTFT) [3,4].
Co-based catalyst is more preferred at LTFT to Fe-based catalyst
while Fe-based catalyst is preferred at high-Temperature Fischer-
Tropsch (HTFT) [6]. In addition, Co-based catalysts have high

http://dx.doi.org/10.1016/j.jece.2016.11.019
2213-3437/ã 2016 Elsevier Ltd. All rights reserved.
 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
selectivity to C5+ linear paraffin hydrocarbons (HCs) and low
selectivity to methanation and water gas shift (WGS) reactions,
making them preferable catalysts for low temperature F-T
synthesis to produce long chain linear hydrocarbons [7].
During the gasification of biomass waste, such as corn cob,
wood biomass, to mention a few, 5–12% CO2 is produced.
Separation of the CO2 from the gasification products to obtain
the syngas required for F-T synthesis requires additional equip-
ment, translating into additional costs. The CO2 could be co-fed
with the syngas stream during F-T synthesis, thereby by-passing
the gas cleaning stage. However, CO2 co-feeding could have
beneficial or detrimental effect on the F-T process, especially on the
reactivity of the catalyst. Therefore, effect of CO2 co-feeding on the
performance of F-T catalyst especially Co-based catalyst needs to
be understood. Against this background, effect of CO2 co-feeding
on the performance of a bi-functional Co/H-ZSM-5 catalyst during
F-T synthesis was investigated in this study. The bi-functional
catalyst, Co/H-ZSM-5, combined F-T synthesis and hydrocracking
together in the same catalyst. The catalyst was synthesized via the
Incipient Wetness Impregnation (IWI) method and the perfor-
mance of the catalyst was tested using a fixed-bed reactor that was
operated as a plug flow reactor (PFR) under steady-state and
isothermal condition. The IWI method was chosen to ensure
moderate Co particle loading and good dispersion within the
support. The H-ZSM-5 zeolite was used as the support because of
its high acidity and good hydrocracking activity.
2. Materials and methods
2.1. Materials
Cobalt (II) nitrate hexahydrate (Co(NO3)26H2O) salt, which was
used as the source of Cobalt (Co) metal, was purchased from
Sigma-Aldrich (Pty) South Africa. Ammonium form of Zeolite
Socony-Mobil-5 (ZSM-5), from which the H-form of Socony-Mobil-
5 (H-ZSM-5) that served as the support for the catalyst was
obtained, was purchased from Zeolyst (USA). Two syngas cylinders
(one with a mixture of H2, CO and N2 and the other with a mixture
of H2, CO, CO2) were purchased from Afrox (Pty) South Africa to
mimic the syngas composition expected from the gasification of
biomass. Nitrogen (N2, 99.99% purity) and Argon (Ar, 99.9% purity)
Fig. 1. Scheme for the synthesis of the Co/H-ZSM-5 catalyst. The same procedure was followed for the preparation of the Co/SiO2 catalyst, except the step that involves the
conversion of ammonium form-ZSM-5 to H-ZSM-5.
55
used as purge gas and carrier gas (for the GC), respectively,
hydrogen and air were purchased from Afrox (Pty) South Africa. All
these materials were used as-supplied without any further pre-
treatment.
2.2. Methods
The catalyst was synthesized using Incipient Wetness Impreg-
nation (IWI) with Cobalt nitrate solution as the precursor for cobalt
using modified technique reported by [4,5]. The solution was
impregnated onto the H-ZSM-5 support; the H-form of ammonium
ZSM-5 zeolite obtained after the calcination of the ammonium
form ZSM-5 at 550  C for 5 h. Cobalt supported on silica catalyst
(Co/SiO2) was prepared and evaluated at the same conditions as
the Co/HZSM-5 catayst for comparison. Scheme of the catalyst
preparation is depicted in Fig. 1.
The techniques employed for the characterization of the
catalyst were: (i) N2 physisorption at 77 K to determine the BET
surface area, pore volume and average pore size of the synthesized
catalyst; (ii) transmission electron microscopy (TEM) that pro-
duces 2-D images to understand the dispersion and the particle
size of the dispersed Co particles; (iii) scanning electron
microscopy equipped with energy-dispersive X-ray (SEM/EDX)
that produces 3-D images to understand the morphology and
elemental composition of the catalyst; (iv) X-ray diffraction (XRD)
to provide information about the crystallinity and phase of the
catalysts; (v) Thermogravimetric analysis (TGA) to understand the
thermal stability of the prepared catalyst; and (vi) H2-Temperature
Programmed Reduction (TPR) to obtain the temperature at which
the prepared catalyst will be completely reducible from in-active
oxide of the metal to active metal phase.
The Nitrogen physisorption experiment was carried using on
about 0.2 g of the catalyst sample on a BET set-up (model:
Micromeritics TriStar 3000 V6.05 A). The samples were degassed at
150  C before nitrogen adsorption experiment was conducted.
Transmission Electron Microscopy analysis was performed using
JEOL 100S FEI (from Field Electron and Ion (FEI) Corporate USA).
About 0.1 mg of the support sample and the catalyst sample were
ultra-sonicated in methanol for 5 min, before placing a drop of the
solution in a copper grid. The Cu-grid with the solution on it was
ventilated and then fed into the TEM chamber for the analysis. X-
56 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
ray diffraction was conducted using Bruker D2 phaser equipped
with a Lynxeye detector at 30 kV and the XRD patterns were
obtained by using a Co-Ka radiation (l = 1.79 Å) in 2u region
between 10 and 90 with a step size of 0.027. The SEM-EDX was
conducted using a Carl-Ziess Sigma Field-Emission-Scanning-
Electron-Microscope (FE-SEM) equipped with Oxford X-act Ener-
gy-Dispersion-Spectroscopy (EDS) detector. The system was
initially purged with Nitrogen gas for about 10 min to remove
air and any other unwanted gases before the analysis. Thermog-
ravimetric analysis was performed on a TGA (model: TA
InstrumentV20.9 Build 20/SDT Q600 equipment using a Universal
V4.7A data handling analysis software). About 10–11 mg of the
sample was analyzed within a temperature range of 25–850  C
with a heating rate of 5  C min
1 under 100 cm3 min
1 air flow. The
H2-TPR was conducted on AutoChem II set-up (model: 2920 V3.05)
from 20  C to 900  C at a temperature ramp of 8  C/min using 5%
ratio of H2 =Ar gas mixture, at a flow of 30 ml/min.
The performance of the synthesized bi-functional catalyst (Co/
H-ZSM-5) was evaluated by using a plug flow reactor (PFR) (see
Fig. 2). The reactor consisted of stainless steel (SS) tubing and
Swagelok fittings. The used reactor was of length 250 mm, internal
diameter (ID) 16 mm and an outer diameter (OD) 20 mm. A frit-disc
with about 1–2 mm diameter holes was fitted inside the reactor to
support the catalyst packing and to prevent the flushing away of
the catalyst particles out of the reactor when operated at a very
high flow rate of the feed. Stainless steel (SS) balls of about 2–5 mm
in diameter each was used to dilute the catalyst particles for
Fig. 2. Experimental setup for performance evaluation of the catalyst.
enhanced uniform heat conduction and distribution in the reactor.
Before catalyst loading, the reactor was cleaned by blowing
pressurized-air through the reactor using an air-gun. This was
done every time when loading the reactor. The SS-balls were
cleaned by using an alcohol then drying them in an oven for about
20–30 min. After cleaning, the quartz wool was then placed on the
frit-disc and ensured that it covered the whole disc surface area.
About 0.5 g of catalyst was loaded into the reactor. The catalyst
was diluted with SS balls to enhance uniform heat transfer within
the reactor and a thermocouple (PT-100) was inserted in the
middle of the reactor and connected to a temperature controller
and indicator to indicate and control the reaction temperature. The
loaded reactor was then connected to the F-T experimental rig and
then pressurized. The experiment proceeded with the catalyst
activated in situ at 30 cm3 STP/min of H2 gas flow and at 330  C for
17–20 h at 8 bar, followed by cooling to room temperature under
the same H2 flow. A rate of 2  C/min and
2  C/min were used for
heating and the cooling steps, respectively. The reactor system was
equipped also with two traps. The first trap was used to trap wax
(Heavy Hydrocarbons) while the second trap was used to capture
oil and water.
The feed and reaction products from the reactor were analyzed
with two pre-calibrated online GCs (Hewlett-Packard 5890
equipped a column (11.5 in. 1/8 in.) packed with Carboxen-
1000,60/80 and a TCD; and a Packard-Bell 433 equipped with a
column (2 m  1/8 in.) packed with Porapaq Q, 80–100 mesh and a
FID). A pre-calibrated offline GC (Varian 3700 equipped with a
 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
column (30 m  0.5 mm  5 mm) packed with Zebron, ZB-1 and a
FID was used for the offline analysis of the reaction products. The
Flame Ionization Detector (FID) used Nitrogen as a courier gas
while the Thermal Conductivity Detector (TCD) used Argon. To feed
the reactor, a two-way valve was used to switch between hydrogen
and synthetic gas during catalyst reduction and catalyst testing,
respectively. Most of the gaseous products (light Hydrocarbons)
were analyzed with the online GCs. The gas lines to the GCs were
heated to 100  C to ensure isothermicity of the reaction. The FID-
GC gas outlet was connected to a flowmeter which was used to
measure the flowrate of the gases. The flowmeter was connected to
a vent to purge out the gases from the system. The GCs were preset
to analyze for an hour at an oven temperature of 200  C and cool to
room temperature for another hour. The GC signals were received
through a transmission box connected to a computer. The CO
conversion, the selectivity of the hydrocarbons in moles and
percentage selectivity (in terms of the total selectivity of all the
hydrocarbon (paraffin and olefin)) were obtained using Eq. (1),
Eq. (2) and Eq. (3), respectively, as reported by [8–10]:
8h


< NCO
bef ore reaction
NCO
af ter reaction NNN2
bef orereaction
COconversion ¼
N2
af ter reaction
: NCO
bef ore reaction
 100%
   The TEM images depicted in Fig. 5 reveal that the Co particles
NHC;i trxn
Selectivity ðmolesÞ ¼ DW

rCo
Nparaf f in;i
%Selectivity ¼  100
Ntotal
paraf f in produced
Where NCO, is the number of mole of CO (mol), and NN2 is the
number of mole of N2 (mol). NHC, is the number of mole of
hydrocarbon (HC) (mol); trxn, the reaction time (hour); DW, is the
catalyst weight (g); and i, is the component. Nparaffin, is the number
of mole of paraffin (mol); Ntotal-paraffin, is the total number of mole
of paraffin produced (mol).
3. Results and discussion
3.1. Catalyst preparation and characterization
The N2 physisorption experiment revealed BET surface area,
pore volume and average pore size of the catalyst to be 292 m2/g,
0.18 cm3/g and 2.83 nm, respectively (see Table 1). In addition, the
results of the N2 physisorption, as presented in Table 1, show that
the BET surface area, the pore volume and the pore size of the
support (H-ZSM-5) were 333 m2/g, 0.23 cm3/g and 3.03 nm,
respectively. The reduction in the BET surface area (from
333 m2/g to 292 m2/g), pore volume (from 0.23 cm3/g to
0.18 cm3/g) and the average pore size (from 3.03 nm to 2.83 nm)
of the H-ZSM-5 support after IWI indicates that Co particles were
successfully impregnated onto the support. From the value of the
average pore size of the catalyst in Table 1, it could be concluded
that the synthesized catalyst consisted of mesopores according to
the definition of mesoporous solids [11].
Table 1
BET surface area, pore volume and pore size of the catalyst and the support.
Materials BET surface area (m2/g)
H-ZSM-5 333
Co/H-ZSM-5 292
57
The XRD patterns depicted in Fig. 3 show that the catalyst
particles were crystalline and this finding is in agreement with
literature [5]. According to Lu et al. [12], ZSM-5 is orthorhombic in
shape. Orthorhombic crystal structures possess Simple Cubic (SC),
Body-Centred (BC) and Face Centred (FC) lattice symmetry [13]. In
the XRD patterns depicted in Fig. 3, the presence of cobalt metal
particles within the Co/H-ZSM-5 is shown with “black-diamond
markers” on the pattern, (topmost XRD pattern in Fig. 3). At 2-u:
36.4, 42.99, 70.01, and 77.51, there were no peaks diffracted for H-
ZSM-5 sample. However after IWI of the cobalt onto the H-ZSM-5,
the resulting catalyst (Co/H-ZSM-5) showed peaks diffracted at the
aformentioned 2-u, indicating that cobalt particles were success-
fully incorporated in the zeolite support.
Fig. 4 shows the SEM/EDX results of the Co/H-ZSM-5 catalyst.
The shape of the Co/H-ZSM-5 catalyst particles, as inferred from
the SEM image (Fig. 4 (top)) is irregular-rounded due to metallic
nature of Cobalt. The image also shows agglomerates of the catalyst
particles. The EDX spectrum (Fig. 4 (botton)) shows that Cobalt
(with electronegativity of about 1.88) was detected at about 0.8 kV
i9 and 7 kV. In addition, the EDX results reveal an estimated
= experimental Co loading of about 25% in the catalyst. This value
; is two times the value reported by Sartipi et al. [5] for IWI of the
cobalt-solution on H-ZSM-5 support because a two-step impreg-
nation method suggested by Sartipi et al. [5] to enhance catalyst
ð1Þ loading in microporous materials such as H-ZSM-5, was used in the
synthesis.
were successfully dispersed within the H-ZSM-5. Fig. 5(a) depicts
ð2Þ
the H-ZSM-5 zeolite support before the impregnation; while
Fig. 5(b) shows that the as-prepared catalyst has Co3O4 embedded
within the support (as indicated with the arrows). By using the
TEM images (Fig. 5) and the XRD patterns (Fig. 3) and following the
ð3Þ
procedure of Guo et al. [14], the size of the metal grains could be
estimated to be about 8  3 nm. The TEM images confirmed that
cobalt oxide particles were successfully impregnated onto the
supports and that the Co particles were uniformly dispersed within
the support. These observations agree well with the observations
reported by Mohanty et al. [15] and Sartipi et al. [5] for their
catalysts prepared using the same method.
The TEM images depicted in Fig. 6 show the morphology of the
traditional Co/SiO2 catalyst used for comparison in this study. The
images show that the Co particles were well dispersed within the
support and the average size of the Co metal particles in the
catalyst could be estimated to be about 15  0.5 nm. In addition,
the EDS analysis conducted on the catalyst sample revealed a
theoretical Co loading of about 20%. For Co/SiO2, average particle
size of 16 nm and 8–35 nm were reported by Sartipi et al. [16], and
Ernest [17], respectively, for Co particles dispersed within their
SiO2 supported catalysts. Therefore, the average particle size of the
Co particles obtained in this study for the synthesized Co/SiO2 is in
good agreement with literature. In addition, the BET surface area of
about 229 cm2/g and pore volume of about 0.9 cm3/g, obtained for
the catalyst agree with the results reported by Sartipi [4].
The TGA plot shown in Fig. 7 reveals that the Co/H-ZSM-5
catalyst was thermally stable up to 500  C. It can be observed from
Fig. 7 that at temperatures below 200  C, a rapid weight loss of
about 5–7% was observed for the catalyst, the support and the
ammonium-form ZSM-5, resulting in a steep slope of the thermal
Pore volume (cm3/g) Average pore size (nm)
0.23 3.03
0.18 2.83
58 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
Fig. 3. XRD Patterns of the Support and the synthesized Co/H-ZSM-5 catalyst.
curve. The steady increase in weight loss from room temperature
to 100  C could be attributed to the loss in moisture content within
the catalyst and some hydration water. At a temperature between
100  C and 150  C, the weight loss could be attributed to the
burning off of the loose organic matter within the catalyst. These
organic matter might have been introduced during the calcination
of the as-prepared catalyst after the synthesis. At a temperature of
150  C, a residual weight of 93 wt.%, 94 wt.% and 95 wt.% was
recorded for H-ZSM-5, ZSM-5 and Co/H-ZSM-5, respectively,
corresponding to a weight loss of 7 wt.% for H-ZSM-5, 6 wt.% for
ZSM-5 and 5 wt.% for Co/H-ZSM-5. As the temperature increased
between 150  C and 200  C the weight loss increased as well.
However at temperatures above 200  C, a slow weight loss was
observed.
After the calcination and during the catalyst synthesis, the
cobalt particles exist as cobalt oxide, and hence reduction is
required to obtain the active elemental Cobalt within the catalyst.
Temperature programmed reduction (TPR) experiment is usually
conducted in the presence of a reducing agent like H2 to investigate
the reducibility of an heterogeneous catalyst. In this study, TPR was
conducted on the Co/H-ZSM-5 catalyst in the presence of H2. The
TPR was conducted from 50  C to 900  C in 5% of H2/Ar. Fig. 8
depicts the H2-TPR profile of the Co/H-ZSM-5 catalyst. The onset
for Co/H-ZSM-5 started at about 180  C and the reduction ended at
about 650  C after peaking at A–D, resulting in a broader overall
peak. At peak labelled A in Fig. 9, tricobalt tetraoxide (Co3O4) was
reduced to Cobalt (II) oxide (CoO) at a temperature of about 272  C.
The Cobalt (II) oxide was then reduced at 302  C to elemental
Cobalt (Co), which was then fully reduced to Co metal at 320  C (as
shown with Peak C), thereby confirming the sequential conversion
of Co3O4 to CoO and CoO to Co [18]. At peak D the elemental Cobalt
binds itself to the zeolite support, forming Co/H-ZSM-5 at peak D.
Hydrogen was highly consumed throughout the reduction process
(180–650  C). The large volume of hydrogen consumed at high
temperatures results in high oxidation states of the cobalt metal
and hence strong interaction of the cobalt metal with the support.
This occurrence could be indicated by the overlapping of peak C
and D [19–21]. Wang et al. [19] have reported the high interaction
 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
Fig. 4. Mophological and elemental composition of Co/H-ZSM-5. SEM image (top); EDX results (bottom).
of metal-support in their catalysts as well. In addition, the high
reduction temperature of metals could be attributed to the high
acidity of the support materials, and this corroborates the results
obtained in this study since the zeolite support is acidic [22]. The
reduction profile also reveals the reduction of another oxide at
500  C (see Peak E) which could be alumina because zeolite is an
aluminous-silicate material. Previous studies have shown that
alumina is reducible at a temperature 500  C [23–25]. Table 2
provides a summary of the TPR results obtained in this study, and
Fig. 5. TEM images of the synthesized bi-functional Co/H-ZSM-5 catalyst. (a) H-
ZSM-5 support and (b) Co/H-ZSM-5.
59
the paths in the reduction of the Co3O4 to Co metal in the presence
of H2 as the reducing agent could be proposed as follows:
Co3O4 ! CoO ! Co.
3.2. Effect of CO2-cofeeding on the performance of the Co/H-ZSM-5
catalyst
Table 3 shows the results obtained from the investigation of the
effect of CO2 co-feeding on the performance of the bi-functional
Co/H-ZSM-5 catalyst. For comparison, the performance of the bi-
functional Co/H-ZSM-5 catalyst was compared with that of the
traditional Co/SiO2 catalyst (also synthesized for comparison) in
the presence of CO2 co-feeding under similar conditions (see
Table 3). The traditional catalyst was prepared via IWI using the
modified synthesis method reported by Guo et al. [14] with an
expected theoretical loading of about 20 wt.% of the Cobalt metal.
A CO conversion of 53.8% was obtained for Co/H-ZSM-5
catalyzed reaction at 250  C, at a Gas Hourly Space Velocity
(GHSV) of 1200 ml h
1 g
1, at a pressure of 15 bar and at a H2/CO
ratio of 2.5 without CO2. When a syngas mixture containing 5% of
CO2 was used, the CO conversion increased to 73.8%. Also the CO2
was hydrogenated to hydrocarbons with a conversion of 63.6% (see
Table 3). Recently, Yao et al. [26] reported CO conversion of about
20% in the presence of 5% of CO2 co-feeding. In addition, the
authors reported about 0.4% CO2 conversion at 200  C, at a pressure
60 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62

it could be speculated that, in the presence of CO2 co-feeding the

Fig. 6. TEM images of the prepared commercial catalyst. (a) SiO2 support and (b)
Co/SiO2.
of 20 bar, at a flowrate of 3600 GHSV and at a H2/CO ratio of 2 for
the Co catalyzed reaction. However in the absence of CO2 co-
feeding, Yao et al. [26] reported a CO conversion of 14.6%, a value
lower than the value obtained in this study (see Table 3). Therefore,
presence of CO2 enhanced the rate at which CO was converted to
products, thereby resulting in a higher CO conversion than the
conversion in the absence of CO2 co-feeding.
Fig. 9 depicts the products of the Co/H-ZSM-5 catalyzed
reaction for a syngas mixture of H2/CO ratio of 2.5 with 0% CO2 and
with 5% CO2 in the feed. It can be observed from Fig. 9, that the
presence of CO2 resulted in a minor or no change in paraffin
selectivity. In the presence of CO2 co-feeding, the selectivity of the
bi-functional Co/H-ZSM-5 catalyst was 53% to methane, 34% to C2,
<4% to C4–C5 and <10% to C6+. These values are more or less the
same as the selectivity to these hydrocarbons (HCs) in the absence
of CO2 co-feeding. Yao et al. [26] reported that paraffin selectivity,
in particular methane, increased with a decrease in CO partial
pressure. In this study the CO partial pressure was kept constant
while the partial pressure of N2 was altered with the introduction
of CO2 gas (changed from 15% to 10% while the CO2 was 5%).
Therefore, the results obtained in this study are in agreement with
the results of Yao et al. with regard to the selectivity to paraffin, in
particular methane [26]. In addition, it was observed that CO2 co-

Fig. 7. Thermogravimetric analysis of the prepared Co/H-ZSM-5 catalyst and the support.

Fig. 8. Temperature programme reduction (TPR) profile of the synthesized Co/H-ZSM-5 catalyst.
 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62 61

Fig. 9. Change in Olefin & Paraffin Selectivity in the absence of CO2 (a) and in presence of CO2 (b). Experimental conditions: H2/CO: 2.5; Temperature: 250  C; Pressure: 15 bar;
GHSV: 1200 ml h
1 g
1; CO2: 5%.

production of paraffin remained the same throughout the reaction

Table 2
duration for Co/H-ZSM-5 catalyzed F-T reaction.
Summary of the TPR of the Co/H-ZSM-5 catalyst.
From Table 3, CO conversion of 73.8% and 70.4% were obtained
Peak Reduction Temperature ( C) Phase for Co/H-ZSM-5 and Co/SiO2 catalysts, respectively, in the presence
A 272 Co3O4 of CO2 co-feeding, making the conversion from the Co/H-ZSM-5
B 302 CoO catalyst to be about 3% higher than that of the traditional Co/SiO2
C 320 Co catalyst. Fig. 10 shows that the selectivity of the bifunctional Co/H-
D 327 Co/H-ZSM-5
E 617 Al2O3
ZSM-5 catalyst to methane was 53% (see Fig. 10(a)). In the presence
of CO2 co-feeding, the CO2 conversion of the bi-functional catalyst
was 63.6% and the traditional Co/SiO2 catalyst displayed CO2
conversion of 75.3%. Most of the CO2 that reacted contributed
feeding influenced the selectivity of the catalyst to olefins as well.
mainly to olefin production; hence a high selectivity of 76% to C6+
The selectivity of C3 olefin decreased from 43% to 35% while C4
olefin was obtained for the Co/SiO2 catalyzed reaction (see
olefin increased from 25% to 32%. Furthermore, the C6+ olefin
Fig. 10(b)), contributing to the CO2 conversion of 75.3%. On the
increased from 9% to 15% when the syngas was co-fed with CO2.
other hand, CO2 reacted when Co/H-ZSM-5 catalyst was used,
However, Yao et al. reported that if the ratio of CO2 to CO in the CO2
yielded almost uniform distribution of C2–C4 olefins.
co-feeding is more less than 50% for a Cobalt catalyzed reaction, the
Comparing the selectivity of the catalysts, Fig. 10(a), (b) shows
CO2 will behave as an inert gas and takes no part in the reaction
that the presence of CO2 in the feed increased the selectivity of Co/
[26]. In contrary to this finding, results from this study show that in
H-ZSM-5 catalyst to olefin with Co/H-ZSM-5 producing more
the presence of CO2 and at a CO2/CO ratio is more less than 50%,
middle olefin hydrocarbons. In addition, the selectivity of Co/SiO2
hydrogenation of CO2 occurred. Therefore, the increase in the
catalyst to lower and middle olefin increased in the presence of CO2
selectivity of the catalyst to higher olefin from 9% to 15% in the
co-feeding, with a slight increase in the paraffin as well. Therefore,
presence of CO2 could be attributed to the speculation that when
for Co/SiO2 catalyzed reaction in the presence of 5% CO2, both C1 to
most of the CO has been hydrogenated to methane and ethane, and
C6+ hydrocarbon selectivity increased with the catalyst displaying
the remaining CO is not enough to produce C3+ paraffin, the
more selective to C6+ olefin. On the contrary, for Co/H-ZSM-5
reaction opted for CO2 to react, thereby resulting in more olefins
catalyzed F-T reaction, an increase in selectivity to olefin resulted
since the CO2 reaction favours olefin production. In addition, Yao
in a decrease or no change in selectivity to paraffin hydrocarbons.
et al. [26] reported a selectivity of 15% to methane in the presence
The CO2 co-feeding only influenced the selectivity of the catalysts
of CO2, but the authors did not separate the hydrocarbons (HCs)
to olefins. Consequently, the selectivity of the Co/H-ZSM-5 catalyst
formed during the reaction, but grouped them together as C2+
to olefins increased while its selectivity to paraffin remained the
hydrocarbons for which 85% selectivity was reported.
same or slightly decreased. Water formation (as a result of water-
It could be concluded that CO2 co-feeding enhances the catalyst
gas-reaction in the process) increased from 0.5 to 1.5 g in the
selectivity to intermediate olefin carbon number and also the CO
absence of CO2 co-feeding to about 2–3.5 g (by weight) for Co/SiO2
conversion. The enhanced CO conversion in the presence of CO2 is
catalyzed reaction in the presence of CO2 co-feeding, contributing
present can be attributed to olefin formation since no change in the
to the higher CO2 conversion observed for Co/SiO2 catalyst. The
paraffin selectivity was observed. Therefore, under similar con-
findings from this study agree well with the results of Dorner et al.
ditions, a syngas with or without CO2 content will offer the same
[27], where water production due to Water-Gas-Shift (WGS)
paraffin selectivity with a higher CO conversion. However, when
reaction in the presence of CO2 was reported.
CO2 was introduced, more olefins were produced but the

Table 3
Effect of CO2 co-feeding on the rate of conversion Co/H-ZSM-5 catalyzed F-T synthesis.

Catalyst H2/CO (%) GHSV (ml h
1 g
1) Temperature ( C) Pressure (bar) % CO Conversion % CO2 Conversion
CO2
Co/H-ZSM-5 2.5 0 1200 250 15 53.7 –
Co/H-ZSM-5 2.5 5 1200 250 15 73.8 63.6
Co/SiO2 2.5 5 1200 250 15 70.4 75.3
62 M.O. Daramola et al. / Journal of Environmental Chemical Engineering 5 (2017) 54–62
Fig. 10. Olefin and Selectivity in the presence of C O2. (a) for Co/H-ZSM-5, and (b) for Co/SiO2 catalyst. Experimental conditions: H2/CO: 2.5; Temperature: 250  C; Pressure:
15 bar; GHSV: 1200 ml h
1 g
1; CO2: 5%.
4. Conclusions
Effect of CO2 co-feeding on the performance of a bifunctional
Co/H-ZSM-5 catalyst and the traditional Co/SiO2 catalyst during F-T
synthesis was evaluated in this study. The effect of CO2 co-feeding
was performed under the process conditions investigated in this
study. Conversion and selectivity results obtained when CO2 was
present in feed were compared to the results obtained in the
absence of CO2. Also the performance of the bi-functional catalyst
was compared to that of a traditional catalyst (also prepared in this
study for comparison) in terms of, which products are favoured as
well as how the conversion of CO was affected. The co-fed CO2 was
converted to hydrocarbons and a CO2 conversion of 63% was
obtained for the bi-functional catalyst. In terms of selectivity, both
syngas (with CO2 co-feeding and without CO2 co-feeding) gave
similar product selectivity to paraffins. The bi-functional catalyst
was 53% selective to methane, 34% to C2, <4% to C3–C5 and less
than 10% selective to C6+ HCs. It was observed that co-feeding CO2
affected the olefin selectivity as well, for most olefin HCs selectivity
increased. However, the C6+ increased from 9% to 15% when the
syngas was co-fed with CO2. It is noteworthy to mention that the
obsereved performance might have been influenced by the type of
support used for the catalysts. Such influence was not considered
in the analysis of the catalyst performance. Future work should
consider the investigation of the influence of catalyst support and
also the long-term operational stability of the bi-functional
catayst.
Acknowledgements
The authors acknowledge the financial support of the National
Research Foundation (NRF) South Africa for KM. Also, MOD
appreciates the financial assistance of iNkwazi through NWU/Wits
research collaboration.
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