Thermal dry reforming of methane over La2O3 co-supported Ni/MgAl2O4 catalyst for hydrogen-rich syngas production

Article abstract of DOI:10.1007/s11164-020-04174-z

The excess emission of greenhouse gases (GHGs) such as CO₂ and CH₄ is posing an acute threat to the environment, and efficient ways are being sought to utilize GHGs to produce syngas (H₂, CO) and lighter hydrocarbons (HCs). In this study, the dry reforming of methane (DRM) has been carried out at 700?°C using La₂O₃ co-supported Ni/MgAl₂O₄ nano-catalyst in a fixed bed thermal reactor. The catalyst is characterized using various techniques such as XRD, FESEM, EDX-mapping, CO₂-TPD, H₂-TPR and TGA. The modified MgAl₂O₄ shows the flake type structure after the addition of La₂O₃. The TPR and TPD analysis shows the highly dispersed metal and strong basic nature of the catalyst?consequently enhances the conversion of CO₂ and CH₄. The highest conversion for CH₄ is 87.3% while CO₂ conversion is nearly 89.5% in 20?h of operation time. The selectivity of H₂ and CO approached 50% making the H₂/CO ratio above unity. In the longer time-on-stream (TOS) test, the catalyst shows elevated potential for longer runs showcasing better catalytic activity. The stability of the catalyst is indicated via a proposed reaction mechanism for DRM in operating conditions. Moreover, TGA indicates the lower weight loss of spent catalyst which ascribed the lower formation of carbon during TOS 20?h.

Full text of DOI:10.1007/s11164-020-04174-z

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-020-04174-z
Thermal dry reforming of methane over La2O3
co‑supported Ni/MgAl2O4 catalyst for hydrogen‑rich syngas
production
Asif Hussain Khoja1 · Mustafa Anwar1 · Sehar Shakir1 ·
Muhammad Taqi Mehran2 · Arslan Mazhar1 · Adeel Javed1 ·
Nor Aishah Saidina Amin3
Received: 27 March 2020 / Accepted: 6 May 2020
© Springer Nature B.V. 2020
Abstract
The excess emission of greenhouse gases (GHGs) such as CO2 and CH4 is posing
an acute threat to the environment, and efcient ways are being sought to utilize
GHGs to produce syngas (H2, CO) and lighter hydrocarbons (HCs). In this study,
the dry reforming of methane (DRM) has been carried out at 700 °C using La2O3
co-supported Ni/MgAl2O4 nano-catalyst in a fxed bed thermal reactor. The cata-
lyst is characterized using various techniques such as XRD, FESEM, EDX-mapping,
CO2-TPD, H2-TPR and TGA. The modifed MgAl2O4 shows the fake type structure
after the addition of La2O3. The TPR and TPD analysis shows the highly dispersed
metal and strong basic nature of the catalyst consequently enhances the conversion
of CO2 and CH4. The highest conversion for CH4 is 87.3% while CO2 conversion is
nearly 89.5% in 20 h of operation time. The selectivity of H2 and CO approached
50% making the H2/CO ratio above unity. In the longer time-on-stream (TOS) test,
the catalyst shows elevated potential for longer runs showcasing better catalytic
activity. The stability of the catalyst is indicated via a proposed reaction mechanism
for DRM in operating conditions. Moreover, TGA indicates the lower weight loss of
spent catalyst which ascribed the lower formation of carbon during TOS 20 h.
Keywords Dry reforming of methane · thermal reactor · MgAl2O4 · H2 production ·
syngas
*
Asif Hussain Khoja
asif@uspcase.nust.edu.pk
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

A. H. Khoja et al.
Introduction
Dry reforming of methane (DRM) (Eq. 1) is an important technique which has been
used to convert the greenhouse gases such as CO2 and CH4 to syngas (H2, CO) and
lighter hydrocarbons (C2-C3) [1]. The syngas can be used as feedstock for the well-
known Fischer–Tropsch (FT) synthesis process in gas-to-liquid fuel technology [2].
The CH4 and CO2 have been successfully converted into fuels via DRM [3], how-
ever, the carbon deposition is a major concern identifed in the recent studies [4, 5].
Mainly, the carbon is formed via two famous reactions which are methane cracking
(Eq. 2) and Boudouard reaction (Eq. 3) [6]. Another issue is the H2/CO ratio, which
is usually less than unity due to the reverse water gas shift reaction (RWGS) (Eq. 4)
[7, 8].
CH4 + CO2 → 2 CO + 2 H2 ΔH◦ = 247kJ mol−1 ( DRM )
(1)
CH4 → C + H2 ΔH◦ = 75kJ mol−1 (Methane cracking)
(2)
2 CO → C + CO2 ΔH◦ = −172 kJ mol−1 (Boudouard reaction)
(3)
CO2 + H2 → CO + H2O ΔH◦ = 41.27 kJ mol−1 (RWGS)
(4)
The aim of developing an efcient and stable catalyst is to improve the conver-
sion efciency, stability and H2/CO ratio with lower carbon formation [9]. Vari-
ous catalyst systems were employed to improve the conversion efciency. The Ni-
based catalyst with various supports such as Al2O3 [10], MgAl2O4 [11], SiO2 [12],
Mesoporous silica molecular sieves (MCM) [13], MgO [14], zeolites [15] and ZrO2
[16] were reported for DRM [17]. Furthermore, co-supported catalysts were also
extensively studied with multiple objectives such as CO2 adsorption and metal dis-
persion [14, 18]. The noble metals demonstrate high catalytic activity as well as
inhibit the coke formation reported in the literature. However, the high cost makes
them less suitable for the commercialization of the DRM process, extensively com-
piled by Pakhare & Spivey [19].
The Ni-based catalysts need further improvements to make them more viable for
the DRM as the carbon growth on Ni sites is the most common issue with the single-
supported catalyst. Recently, the co-support system with Ni as active metal is seek-
ing remarkable attention such as Al2O3-MgO [20]. To achieve the communal efect
of both Al and Mg, the Ni/MgAl2O4 spinel has been synthesized for DRM, and it
resulted in a stable and enhanced performance than Ni/Al2O3. However, issues such
as carbon formation and H2/CO ratio were not resolved [21, 22]. The catalyst perfor-
mance in the DRM also depends on the physicochemical properties of the material.
The physicochemical properties of catalyst can be modifed by the preparation tech-
niques and by introducing a co-support which will improve the basicity and metal
dispersion on the catalyst support [23–25]. The basic nature of the catalyst is also
important for carbon deposition and deactivation of the catalytic performance [26,
27]. Ni interface with MgAl2O4 is improved by the communal efect of MgAl2O4
1 3

Thermal dry reforming of methane over La2O3 co-supported…
and La2O3 as mixed matrix support [28]. In thermo-catalytic DRM, the combined
efect of La2O3 and MgAl2O4 catalyst is barely reported [29].
Herein, we investigate the Ni/La-Mg catalyst for high-temperature DRM to ana-
lyse the catalytic activity, products distribution and stability during the long-term
continuous operation. We prepared the mixed-matrix support nano-catalyst of 10
wt.% Ni/La2O3-MgAl2O4 and tested for DRM in a fxed bed thermal reactor. The
catalyst material was characterized by X-ray difraction (XRD), feld emission elec-
tron microscopy (FESEM), H2 temperature-programmed reduction (H2-TPR), CO2
temperature-programmed desorption (CO2-TPD), N2 adsorption–desorption (BET)
EDX-mapping and TGA. Finally, a probable reaction mechanism was proposed
based on product distribution.
Materials and methods
Material synthesis and characterization
MgAl2O4 and La2O3 spinal was prepared by modifying the co-precipitation method
followed by hydrothermal process reported elsewhere [30]. For MgAl2O4 the
respective nitrate salts were added to ammonia solution with a ratio of 2:1 (Al: Mg).
The required quantities of citric acid and dimethylformamide (DMF) were added
to improve the metal dispersion and better crystal growth. The solution was kept at
160 °C for 24 h in an autoclave for the hydrothermal process. The slurry was then
washed several times using ethanol and DI water, and the samples were dried in
an oven. The same method is repeated for the synthesis of La2O3. For co-support,
MgAl2O4 and La2O3 were taken as 4:1 (wt. ratio) as co-support and prepared by
microemulsion technique [31]. The 10% wt. Ni as the active metal was impregnated
by the modifed incipient wetness impregnation method [32]. The catalyst was then
calcined at 700 °C for 3 h in a mufe furnace. The material was characterized by
XRD, FESEM, H2-TPR, CO2-TPD, EDX-mapping, BET and TGA. The characteri-
zation methods and equipment details were reported elsewhere [32]. The crystal-
lography and morphology of the catalyst were analysed by XRD, FESEM and BET.
The crystallite size was calculated using the Scherrer equation [32, 33]. The metal-
support interaction and basicity of the materials were analysed by TPR and TPD,
and TGA was used to explain the thermal stability of the synthesized material.
Experimental setup and calculations
The experimental setup for the fxed-bed thermal reactor is presented in Fig. 1. Briefy,
the feed gases CH4 (99.99%) and CO2 (99.99%) controlled by a mass fow controller
(ALICAT) were provided to the fxed bed reactor. The fxed-bed reactor consists of a
vertical furnace (Carbolite UK) integrated with a thermocouple. The catalyst is loaded
in alumina tube (10 mm inner diameter) with the help of quartz wool. A condenser
and silica-bed are used to separate the liquid and gaseous products, respectively, before
sending the syngas to the gas analysis systems. The products gases were analysed using
1 3

A. H. Khoja et al.
Fig. 1 Experimental setup for thermal catalytic dry reforming of methane
an online gas chromatograph (GC) (Agilent 6890 N) equipped with a thermal conduc-
tivity detector (TCD) and fame ionization detector (FID) [29].
The catalytic activity tests were conducted to analyse the performance of the DRM
catalyst in a fxed-bed thermal reactor. The reactant conversion (X) and selectivity (S)
were calculated according to Eqs. (5–9). When n represents the number of moles of the
individual species. The experiments were repeated twice to determine the relative error.
[
]
(
)
( nCH4)converted
(nCH4)feed
CH4 conversion XCH % =
× 100
(5)
(6)
(7)
(8)
(9)
4
[
]
(
)
(n CO2)converted
(n CO2)feed
CO2 conversion XCO % =
× 100
2
[
]
(nCO) produced
(
)
CO selectivity SCO % =
× 100
( nCH4 + nCO2)converted
[
]
(nH2)produced
(
)
H2 selectivity SH % =
× 100
2
(2 × nCH4)converted
[
]
(2 × nC2H6)produced
(
)
C2H6 selectivity SC H % =
× 100
2
6
(nCH4 + nCO2)converted
1 3

Thermal dry reforming of methane over La2O3 co-supported…
Results and discussion
Physicochemical properties of the material
The crystallographic structure of the prepared catalysts was analysed by X-ray
difraction (XRD) as shown in Fig. 2a. The X-ray difraction peaks for MgAl2O4
Fig. 2 a XRD of the prepared samples b H2-TPR with inset H2 uptake profle and
1 3

A. H. Khoja et al.
(PDF#72–6947) were analysed, and the cubical phase (hkl; 311) was confrmed at
38.5° with a space group of 227: Fd3m [24, 34]. The average crystallite size for
MgAl2O4 was 10.5 nm. Similarly, La2O3 (71–5408) was detected in XRD analy-
sis with a major peak at 30.3° (hkl;011) with an average crystallite size of 9.7 nm
[35]. The NiO (PDF#44–1159) with major phase (101) was confrmed at 37.5° hav-
ing an average crystallite size of 10.0 nm [32]. The major peak of NiAl2O4 (PDF
#10–0339) was detected at 37.09° (311) with a crystallite size of 14.3 nm [36] and
LaNiO3 peak (PDF #33–0710) at 23.08° (100) while the crystallite size is 13.8 [37]
with rhombohedral structure.
The reduction behaviour of the developed DRM catalyst was analysed using
H2-TPR technique depicted in Fig. 2b for the La2O3 co-supported Ni/MgAl2O4 cal-
cined at 700 °C. The TPR shows the frst major peak at 552 °C with the H2-uptake
of 249.3 μmol g−1 while the second major peak was detected at 695 °C showing
H2-uptake of 596.6 μmol g−1. The total H2-uptake of~850 μmol g−1 which shows
the 91% degree of reduction [38]. The higher H2 uptake at elevated temperature
shows the good interaction of Ni/La2O3-MgAl2O4.From the intense TPR peak at
695 °C, it is evident that NiO has been reduced into Ni [39].
The basicity of MgAl2O4 and Ni/La2O3-MgAl2O4 is investigated using CO2-TPD
and presented in Fig. 3 and Table 1. Three diferent peaks present at various regions
from weak to strong basic nature of the prepared catalyst. The frst two peaks for
MgAl2O4 at 87 °C and 291 °C with CO2 uptake of 347 μmol g−1 and 122 μmol g−1,
respectively, and indicating the weak basic sites [11]. While for Ni/ La2O3-MgAl2O4
sample, the frst two peaks were detected at 95 °C and 361 °C with CO2 uptake
of 206 μmol g−1 and 110 μmol g−1, ascribed to the weak and medium basic sites,
respectively. The distant peak shift from weak region to the medium is due to the
addition of La2O3. The strong basic sites for MgAl2O4 were detected at 542 °C
10% Ni/La2O3-MgAl2O4
681
MgAl2O4
361
95
542
291
87
100
200
300
400
500
600
700
800
Temperature oC
Fig. 3 CO2 TPD analysis of La2O3 co-supported Ni/MgAl2O4 and MgAl2O4 with inset CO2 uptakes
1 3

Thermal dry reforming of methane over La2O3 co-supported…
Table 1 CO2 uptake for
Peak #
Sample
Temperature CO2 uptake
MgAl2O4 and 10% Ni/La2O3-
MgAl2O4
(°C)
(μmol g−1
)
1
2
3
MgAl2O4
10% Ni/La2O3-MgAl2O4
MgAl2O4
10% Ni/La2O3-MgAl2O4
MgAl2O4
10% Ni/La2O3-MgAl2O4
80
85
291
301
542
681
347
206
121
110
462
683
having the CO2 uptake of 463 μmol g−1 [11]. In contrast, for Ni/La2O3-MgAl2O4
sample, the strong basic sites were present at 681 °C with the CO2 uptake of
683 μmol g−1. The higher CO2 uptake at the elevated temperature depicted the
strong basic nature of the catalyst which is suitable for the DRM process and it is
expected to exhibit better coke resistance during the long-term TOS tests [40].
The morphology of the prepared DRM catalysts was analysed by FESEM and
depicted in Fig. 4. The MgAl2O4 sample shows agglomerated porous structure pre-
sented in Fig. 4a and La2O3 shows a uniform web-like structure is evident in the
Fig. 4 FESEM micrographs of a MgAl2O4 b La2O3 c La2O3 co-supported Ni/MgAl2O4 d TGA of La2O3
co-supported Ni/MgAl2O4
1 3

A. H. Khoja et al.
modifed preparation method using DMF as a surfactant which also assists in the
uniform crystal growth (Fig. 4b). La2O3 co-supported Ni/MgAl2O4 sample resulted
in a nanofake-type structure depicted in Fig. 4c. The irregular structure of MgAl2O4
is modifed by web-like La2O3 infusing with the Ni particles. Furthermore, the ther-
mal stability of the La2O3 co-supported Ni/MgAl2O4 presented in Fig. 4d. The total
weight loss is less than 3.5% in the temperature range of 125 °C is ascribed to the
removal of moisture [41].
The N2 adsorption–desorption isotherms, surface area (SBET), average pore
volume (Vpore) and average pore radius is presented in Fig. 5. The samples exhib-
ited type IV isotherm confrming the formation of mesoporous structure material
for all the synthesized samples. The surface area of MgAl2O4 and La2O3 was 102
m2 g−1and 41.3 m2 g−1, respectively. While the addition of Ni into La2O3-MgAl2O4
reduces the surface area to 90 m2 g−1. It is ascribed to the infusion of Ni particle on
the surface of the catalyst support. The average pore radius of the MgAl2O4, La2O3
and Ni/La2O3-MgAl2O4 is 8.6 nm, 5.7 nm and 8.1 nm, respectively.
Catalyst performance analysis
The DRM activity test has been carried outing using the developed catalyst shown
in Fig. 6. At frst, the DRM was carried without a catalyst which shows very low
catalytic activity. The conversion of CH4 and CO2 is just below 10% at 700 °C. The
selectivity of H2 and CO is found to be less than 6%. In contrast, adding MgAl2O4
catalyst in the fxed bed, the increment in the conversion and selectivity of the prod-
uct is observed. The conversion of CH4 and CO2 is 35% and 32%, respectively. The
selectivity H2, CO and C2H6 is less than 12%, 15% and 3.5% respectively. The Ni
impregnation in MgAl2O4 further improves the catalytic activity with the increase
Fig. 5 N2 adsorption–desorption of prepared samples with inset specifc surface area (SBET) m2 g−1, aver-
age pore volume (Vpore) cm3 g−1 and average pore radius (nm)
1 3

Thermal dry reforming of methane over La2O3 co-supported…
100
XCH (%),
XCO (%)
4
2
SH (%),
SCO (%)
2
80
60
40
20
0
SC H (%)
2
6
4
t
O
2
s
4
y
l
4
O
l
O
l
a
2
t
l
2
A
a
g
A
-MgA
3
C
g
M
o
M
O
2
/
N
i
a
N
L
/
i
N
Fig. 6 Catalysts performance evaluation: GHSV=1500 h−1, catalyst loading=0.3 g, feed ratio (CO2/
CH4)=1, reaction temperature=700 °C, reaction time=2 h
in the conversion of CH4 and CO2 to 65 and 63%. Ni /MgAl2O4 also substantially
improves the selectivity of H2, CO and C2H6 to 32%, 35% and 7.5% as depicted
in Fig. 6. Whereas, incorporating 20% La2O3 as co-support into 10%Ni/MgAl2O4
enhances the conversion of CH4 and CO2 to 87.3% and 89.5%, respectively. The
selectivity of the H2 improves from 32 to 51% for the composite La2O3 co-supported
Ni/MgAl2O4 catalyst. CO selectivity is recorded 46% which is less than the selectiv-
ity of H2. In contrast, C2H6 selectivity decrease to 4.5% in the La2O3 co-supported
Ni/MgAl2O4. This might be due to the higher yield and inhibition of methyl radical
recombination [23].
The overall catalytic activity of the reported samples is in such order:
MgAl2O4 <Ni/MgAl2O4 <La2O3 co-supported Ni/MgAl2O4. The non-co-supported
catalyst activity is lower than that of Co-supported catalyst, which ascribes the
occurrence of reverse water gas shift (RWGS) reaction is limited [23]. The La2O3
co-supported catalyst resists the progress of RWGS and H2 selectivity is improved.
Furthermore, the possible formation of La2O2CO3 inhibit the carbon formation and
improves the catalyst activity [23]. The improvement in the CH4 conversion is due
to the good formation of active sites as depicted in H2-TPR results. The bulk forma-
tion of active sites activates CH4 and resist the CxHx recombination by a further
breakdown.
The comparison with the literature is drawn in Table 2 for the reference. As we
can see that the majority of the reports shows the H2/CO ratio below 1.0 except
for Ni/h-BNNs catalyst reported by [42]. The higher H2/CO ratio depicts the CH4
decomposition or Boudouard reaction. These reactions usually occur on Ni active
1 3

A. H. Khoja et al.
1 3

Thermal dry reforming of methane over La2O3 co-supported…
sites and block them, however, if α-C is formed, it can be easily gasifed or reacts
with La2O3 to form La2O2CO3[23, 42]. The addition of La2O3 also assists the chem-
isorption of CO2 and regeneration of active metal and La2O3 along with major sup-
port MgAl2O4 [23, 24].
Catalyst stability and reaction mechanism
The catalyst stability is one of the most important parameters after the fundamental
catalytic performance. Herein, the La2O3 co-supported Ni/MgAl2O4 was tested for
20 h of time on stream (TOS) test keeping the process parameters constant. The
conversion of CH4 is shown in Fig. 7a, a stable trend having only 03% reduction
in 20 h of TOS observed. Similarly, CO2 also shows the same trend in the same
TOS and experimental conditions. The stable conversion in the reported TOS for
both reactants is encouraging for the reported catalyst. The selectivity of the H2 and
CO partly declined during the 20 h TOS presented in Fig. 7b. The selectivity of
the C2H6 is slightly higher in the 20 h TOS. Figure 8 shows that the H2/CO ratio is
above unity during the 20 h TOS indicating the low carbon formation over the cata-
lyst and enhanced stability.
The conversion stability of the developed catalyst is associated with better metal-
support interaction (MSI high active sites and high basicity due to the addition of
La2O3. It also supports methane activation as well as CO2 adsorption due to its basic
nature [46]. The CH4 activation is due to the Ni and formed Ni-C and 2H2 (Eq. 10).
The formation of La2O2CO3 intermediate carbonate during the adsorption of CO2
(Eq. 11) and after reaction with C-Ni to regenerate the La2O3, Ni and CO resist the
carbon deposition on the catalyst surface (Eq. 12) [47]. The schematic representa-
tion of the reaction mechanism is proposed in Fig. 9.
CH4 + Ni → C − Ni + 2H2
(10)
CO2 + La2O3 → La2O2CO3
(11)
C − Ni + La2O2CO3 → La2O3 + Ni + 2CO
(12)
Characterization of the spent catalyst
After 20 h of TOS, the spent catalyst has been characterized by EDX mapping and
TGA. Figure 10a presented elemental mapping shows the formation of carbon over
the surface of the catalyst. The mapping indicates the formation of carbon is not in
the bulk form (Fig. 10b). The inset FESEM shows the formation of carbon nanof-
bres on the surface of the spent catalyst. The carbon nanofbres can easily reduce in
the gasifcation process and formed CO or CO2.
The TGA profle of the spent La2O3 co-supported Ni/MgAl2O4 after 20 h of TOS
shows the total weight loss of 9–10%, which confrms the formation of a lower amount
1 3

A. H. Khoja et al.
Fig. 7 Efect of time on stream a conversion of reactants (Xn) b H2, CO and C2H6 selectivity (Sx) over
La2O3 co-supported Ni/MgAl2O4; GHSV=1500 h−1, catalyst loading=0.3 g, feed ratio (CO2/CH4)=1,
reaction temperature=700 °C
of carbon. The moisture and volatile matter removal are at 200 °C [11, 48] presented in
Fig. 11. The weight loss in between 200–500 °C is associated with the fbrous carbon
which is referred as β-carbon, as well as the decomposition of La-hydroxide intermedi-
ate phase which is usually formed under the moist conditions due to RWGS [29]. The
total of 3% weight loss between 500–900 °C (Column III-IV) which confrm the low
1 3

Thermal dry reforming of methane over La2O3 co-supported…
1.4
1.2
1.0
0.8
H2/CO ratio
0.6
0.4
0
2
4
6
8
10
12
14
16
18
20
Time on stream (h)
Fig. 8 Time on stream vs H2/CO ratio over La2O3 co-supported Ni/MgAl2O4; GHSV=1500 h−1, catalyst
loading=0.3 g, feed ratio (CO2/CH4)=1, reaction temperature=700 °C
Fig. 9 Proposed reaction mechanism for La2O3 co-supported Ni/MgAl2O4 based DRM
formation of carbon after 20 h TOS. This reduction is also ascribed to the dissociation
of La2O2CO3 [49]. The carbon formed above 700 °C is ascribed to flamentous carbon
(γ-C).
1 3

A. H. Khoja et al.
Fig. 10 a EDX mapping of spent catalyst b EDX elemental analysis with inset FEESEM
Fig. 11 TGA profle of spent La2O3 co-supported Ni/MgAl2O4 after 20 h TOS
1 3

Thermal dry reforming of methane over La2O3 co-supported…
Conclusions
The synthesized La2O3 co-supported Ni/MgAl2O4 has been characterized using var-
ious techniques and employed for the DRM in thermal fxed bed reactor. The cata-
lyst shows enhanced performance and higher H2/CO ratio, much suitable feedstock
for downstream chemicals. The enhanced performance is ascribed to the suitable
physicochemical properties of a catalyst such as metal-support interaction and the
strong basic nature with well-structured morphology. While testing for longer runs,
the catalyst shows stability for 20 h with less than 3% declined in the DRM activity
and TGA of spent catalyst confrms the lower formation of carbon. This stability
suggests the potential of the upgradation of the developed catalyst for the DRM pro-
cess for industrial-scale production of syngas.
Authors Contibution
Asif Hussain Khoja and Nor Aishah Saidina Amin develop the conceptualization of
the work and drafted the manuscript. Arslan Mazhar assisted in material synthesis
and in conducting the experiments. Mustafa Anwar and Sehar Shakir workout the
material characterization analysis. Muhammad Taqi Mehran assisting in the result
analysis of GC, drafting and revising the manuscript.
Acknowledgements The authors would like to extend their deepest appreciation to the Universiti
Teknologi Malaysia for the fnancial support of this research under RUG (Research University Grant,
Vot13H35) and FRGS-MRSA grant.
References
1. J.A. Frankel, Greenhouse Gas Emissions (Brookings Institution, Washington, D.C, 1999)
2. A. Rafee, K. Rajab Khalilpour, D. Milani, M. Panahi, J. Environ. Chem. Eng. 6(5), (2018)
3. R. Dębek, K. Zubek, M. Motak, P. Da Costa, T. Grzybek, Res. Chem. Intermed. 41(12), (2015)
4. A.H. Khoja, M. Tahir, N.A.S. Amin, Energy Convers. Manag. 183, (2019)
5. M.A. Gerber, Review of Novel Catalysts for Biomass Tar Cracking and Methane Reforming (Pacifc
Northwest National Laboratory Richland, WA, USA, 2007)
6. Y.H. Hu, E. Ruckenstein, Adv. Catal. 48(49), (2004)
7. B. Abdullah, N.A.A. Ghani, D.V.N. Vo, J. Clean. Prod. 162, (2017)
8. E. Horvath, K. Baan, E. Varga, A. Oszko, A. Vago, M. Toro, A. Erdohelyi, Catal. Today 281, (2017)
9. M. Usman, W.M.A.W. Daud, H.F. Abbas, Renew. Sustain. Energy Rev. 45, (2015)
10. K. Selvarajah, N.H.H. Phuc, B. Abdullah, F. Alenazey, D.-V.N. Vo, Res. Chem. Intermed. 42(1),
(2016)
11. I.H. Son, S. Kwon, J.H. Park, S.J. Lee, Nano Energy 19, Supplement C (2016)
12. S. Tomiyama, R. Takahashi, S. Sato, T. Sodesawa, S. Yoshida, Appl. Catal. A Gen. 241(1–2),
(2003)
13. H. Arbag, S. Yasyerli, N. Yasyerli, G. Dogu, Int. J. Hydrog. Energy 35(6), (2010)
14. Y.J.O. Asencios, E.M. Assaf, Fuel Process. Technol. 106, (2013)
15. P. Frontera, A. Aloise, A. Macario, F. Crea, P.L. Antonucci, G. Giordano, J.B. Nagy, Res. Chem.
Intermed. 37(2), (2011)
16. N. Rahemi, M. Haghighi, A.A. Babaluo, M.F. Jafari, P. Estifaee, J. Ind. Eng. Chem. 19(5), (2013)
17. V. Sadykov, V. Rogov, E. Ermakova, D. Arendarsky, N. Mezentseva, G. Alikina, N. Sazonova, A.
Bobin, S. Pavlova, Y. Schuurman C. Mirodatos, Thermochim. Acta 567, (2013)
1 3

A. H. Khoja et al.
18. S.H. Zeng, L. Zhang, X.H. Zhang, Y. Wang, H. Pan, H.Q. Su, Int. J. Hydrog. Energy 37(13), (2012)
19. D. Pakhare, J. Spivey, Chem. Soc. Rev. 43(22), (2014)
20. L. Zhang, Q. Zhang, Y. Liu, Y. Zhang, Appl. Surf. Sci. 389, Supplement C (2016)
21. S. Dash, R.K. Sahoo, A. Das, S. Bajpai, D. Debasish, S.K. Singh, J. Alloys Compd. 726, Supple-
ment C (2017)
22. H.-J. Kim, E.-H. Yang, Y.S. Noh, G.H. Hong, J.I. Park, S.A. Shin, K.-Y. Lee, D.J. Moon, Res.
Chem. Intermed. 44(2), (2017)
23. X.Y. Li, D. Li, H. Tian, L. Zeng, Z.J. Zhao, J.L. Gong, Appl. Catal. B-Environ. 202, (2017)
24. A.S. Al-Fatesh, M.A. Naeem, A.H. Fakeeha, A.E. Abasaeed, Chin. J. Chem. Eng. 22(1), (2014)
25. M.A. Uzair, A. Waqas, A.H. Khoja, N. Ahmed, Energy Source Part A 38(24), (2016)
26. A.H. Khoja, M. Tahir, N.A.S. Amin, A. Javed, M.T. Mehran, Int. J. Hydrog. Energy 45(22), (2020)
27. R. Pereñiguez, V.M. Gonzalez-delaCruz, A. Caballero, J.P. Holgado, Appl. Catal. B: Environ. 123,
(2012)
28. D.X. Li, P. Pirouz, A.H. Heuer, S. Yadavalli, C.P. Flynn, Philos. Mag. A 65(2), (1992)
29. A.H. Khoja, M. Tahir, N.A.S. Amin, Energy Convers. Manag. 144, (2017)
30. A. Samad, K.Y. Lau, I.A. Khan, A.H. Khoja, M.M. Jafar, M. Tahir, J. Phys. Chem. Solids 120,
(2018)
31. M. Usman, W.M.A.W. Daud, RSC Adv. 6(44), (2016)
32. A.H. Khoja, M. Tahir, N.A.S. Amin, Fuel Process. Technol. 178, (2018)
33. A.H. Khoja, M. Tahir, N.A. Saidina Amin, Energy Fuels 33(11), (2019)
34. S. Sokolov, E.V. Kondratenko, M.M. Pohl, A. Barkschat, U. Rodemerck, Appl. Catal. B-Environ.
113, (2012)
35. D. Ağaoğulları, İ. Duman, M.L. Öveçoğlu, Ceramics Int. 38(8), (2012)
36. N. Sahli, C. Petit, A.C. Roger, A. Kiennemann, S. Libs, M.M. Bettahar, Catal. Today 113(3), (2006)
37. X. Song, X. Dong, S. Yin, M. Wang, M. Li, H. Wang, Appl. Catal. A Gen. 526, (2016)
38. A. Bordoloi, S. Das, R. Goyal, R.K. Singha, C.R. Pendem, S.K.L. Narayan, R. Bal, V.V.D.N. Prasad,
N.N. Botcha, M. Kumar, (Google Patents, 2017)
39. J. Shen, A.A.C. Reule, N. Semagina, Int. J. Hydrog. Energy 44(10), (2019)
40. S. Das, M. Sengupta, J. Patel, A. Bordoloi, Appl. Catal. a-Gen. 545, Supplement C (2017)
41. J. Guo, H. Lou, H. Zhao, X. Zheng, React. Kinet. Catal. Lett. 84(1), (2005)
42. Y. Cao, P. Maitarad, M. Gao, T. Taketsugu, H.R. Li, T.T. Yan, L.Y. Shi, D.S. Zhang, Appl. Catal.
B-Environ. 238, (2018)
43. R.O. da Fonseca, R.C. Rabelo-Neto, R.C.C. Simões, L.V. Mattos, F.B. Noronha, Int. J. Hydrog.
Energy 45(8), (2020)
44. U. Guharoy, E. Le Sache, Q. Cai, T.R. Reina, S. Gu, J. CO2 Util. 27, (2018)
45. T. Zhang, Z. Liu, Y.-A. Zhu, Z. Liu, Z. Sui, K. Zhu, X. Zhou, Appl. Catal. B: Environ. 264, (2020)
46. L. Zhang, X. Wang, C. Chen, X. Zou, X. Shang, W. Ding, X. Lu, RSC Adv. 7(53), (2017)
47. J.K. Xu, W. Zhou, J.H. Wang, Z.J. Li, J.X. Ma, Chin. J. Catal. 30(11), (2009)
48. C.C. Chong, Y.W. Cheng, H.D. Setiabudi, N. Ainirazali, D.-V.N. Vo, B. Abdullah, Int. J. Hydrog.
Energy 45(15), (2020)
49. E.P. Komarala, I. Komissarov, B.A. Rosen, Catalysts 10(1), (2019)
Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published
maps and institutional afliations.
Afliations
Asif Hussain Khoja1 · Mustafa Anwar1 · Sehar Shakir1 ·
Muhammad Taqi Mehran2 · Arslan Mazhar1 · Adeel Javed1 ·
Nor Aishah Saidina Amin3
1
Fossil Fuel Laboratory, Department of Thermal Energy Engineering, U.S.-Pakistan Centre
for Advanced Studies in Energy (USPCAS-E), National University of Sciences and Technology
(NUST), H-12 Sector, Islamabad 44000, Pakistan
1 3

Thermal dry reforming of methane over La2O3 co-supported…
2
Department of Chemical Engineering, School of Chemical and Materials Engineering (SCME),
National University of Sciences and Technology (NUST), H-12 Sector, Islamabad 44000,
Pakistan
3
Chemical Reaction Engineering Group (CREG), School of Chemical and Energy Engineering,
Faculty of Engineering, Universiti Teknologi Malaysia (UTM), 81310 Skudai, Johor Bahru,
Malaysia
1 3