SYNGAS PRODUCTION BY DRY REFORMING OF METHANE OVER CO-PRECIPITATED CATALYSTS

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International Journal of Advanced Research in Engineering and Technology
(IJARET)
Volume 6, Issue 11, Nov 2015, pp. 01-17, Article ID: IJARET_06_11_001
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ISSN Print: 0976-6480 and ISSN Online: 0976-6499
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___________________________________________________________________________
SYNGAS PRODUCTION BY DRY
REFORMING OF METHANE OVER CO-
PRECIPITATED CATALYSTS
Sanjay P. Gandhi and Sanjay S. Patel
Institute of Technology, Nirma University,
Ahmadabad, Gujarat, India
ABSTRACT
The syngas manufacturing from the reforming of methane with carbon
dioxide is tempting because of output in terms of extra pure synthesis gas and
lower H2 to CO ratio than other synthesis gas production methods like either
partial oxidation or steam reforming. For production of long-chain
hydrocarbons though the Fischer-Tropsch synthesis, lower H2 to CO ratio is
required and important, as it is a most likely feedstock. In recent decades, CO2
utilization has become more and more important in view of the emergent
global warming phenomenon. On the environmental point of view, methane
reforming is tantalizing due to the reduction of carbon dioxide and methane
emissions as both are consider as dangerous greenhouse gases.
Commercially, as cost effectively, nickel is used for methane reforming
reactions due to its availability and lower cost compared to noble metals.
Number of catalysts endures rigorous deactivation because of carbon
deposition. Mainly carbon formation is because of methane decomposition
and CO disproportionate. It is important and required to recognize essential
steps of activation and conversion of CH4 and CO2 to design catalysts that
minimize deactivation. Effect of promoters on activity and stability were
studied in the detail. In order to develop the highly active with minimum coke
formation the alkali metal oxides and ceria/zirconia/magnesia promoters were
incorporated in the catalysts. The influence of ZrO2, CeO2 and MgO, in the
performance of Ni-Al2O3 catalyst, prepare by co-precipitation method was
studied in detailed. The XRD, FTIR, and BET and reactivity test for different
promoted and unprompted catalyst was carried out.
Key words: CH4/CO2 reforming, percentage of Ni loading, Coke formation,
FTIR.
Cite this Article: Sanjay P. Gandhi and Sanjay S. Patel. Syngas Production by
Dry Reforming of Methane over Co-Precipitated Catalysts. International

Journal of Advanced Research in Engineering and Technology, 6(11), 2015,
pp. 01-17.
http://www.iaeme.com/IJARET/issues.asp?JType=IJARET&VType=6&IType=11
1. INTRODUCTION
Utilization of CO2, via a reaction with CH4 to produce a mixture of CO and H2 known
as “synthesis gas” and process is called as dry reforming of methane (DRM) [1].
DRM reaction requires high temperature as reactions are extremely endothermic. The
DRM process provides several advantages over steam reforming of methane and out
of which the most important one is the production of syngas with a low H2/CO ratio,
is suitable for use in forming higher levels alcohols. Typical application is production
of methanol and fischer-tropsch synthesis H2/CO is required around 1, that can be
produced by DRM [2, 3]. DRM is also impact on environmental front, as methane and
carbon dioxide are greenhouse gases. Feedstock’s like biogas, coal bed methane, and
natural gas with high CO2 and CH4 and are good candidates for dry reforming of
methane. CO2 reforming of methane is an interesting route for converting natural gas
into synthesis gas, which can produce clean fuels and other chemicals. The increase in
the known reserves of natural gas and the feasibility of exploring natural reserves in
remote locations several kilometers from coast and in small fields stimulate the
development of gas to liquids technology. Reaction 1 is main reaction out of number
of reactions of DRM.
The reverse water gas shift reaction (RWGS(2)), the Boudouard reaction (3), and
the methane decomposition reaction (4) are side reactions in reforming:
In DRM reaction, there is RWGS reaction (2), in which production of CO form
consumption of CO2 and H2. Because of RWGS reaction the overall CO2 conversion
greater than CH4. Carbon deposition via boudouard reaction (3) and methane
decomposition (4) can deactivate the catalyst are major problems in catalytic CO2
reforming.
Noble metal catalysts have good resistance against coke formation, but their high
price and limited availability prevent their practical application [2-4]. Thermodynamic
experiments have confirmed the inevitable occurrence of carbon formation over a
wide range of catalysts, especially Ni-based ones. On the other hand, higher
conversion attained at high temperatures results in sintering of Ni particles. In dry
reforming of methane nickel based catalyst have been widely used, However, reaction
suffers from low catalytic activity and instability against coke deposition due to the
boudouard reaction and the methane decomposition reaction [1]. Even though Ni

Syngas Production by Dry Reforming of Methane over Co-Precipitated Catalysts
based catalyst are first in choice for the CO2 reforming due to its activity and
reasonable price [4, 5]. Basically, support selection is important, as control of the Ni-
support interactions can improve Ni-catalyst activities in CO2 reforming. High
mechanical strength, high surface area, and the low price of alumina make it a suitable
for Ni-based catalyst. A wide range of basic promoters, such as La2O3, MgO, CaO,
SiO2 have been investigated to develop more stable supports [1]. The catalyst supports
and its preparation methods can influence the activity of catalyst. The present work
investigates activity of promoted and un-promoted catalyst prepared by co-
precipitation for DRM reaction.
2. EXPERIMENTAL
2.1. Catalyst Preparation
Co-precipitation method was used to prepare nickel catalyst promoted with ziroconia,
cerioum and magnesia. Required amount of nickel nitrate, zirconyl nitrate, cerium
nitrate, magnesium nitrate, aluminum nitrate, dissolved in distilled water separately as
per stoichiometric quantities.
The solution were prepared separately and then mixed in a volume proportion
corresponding to the final composition of the catalysts to be obtained. The resulting
solution was stirred and heated in a beaker. The aqueous 1M Na2CO3 solution was
added drop-wise to the nitrate solution under vigorous stirring until pH 10 was
attained at 333 K temperature. The precipitation was allowed to age for 1 h at room
temperature with stirring. The excess solution was removed by filtration. The
precipitate was washed by double distilled water at a room temperature followed by
several times by double distilled water at room temperature in order to remove the
sodium salts. The drying was carried out at 373 K for overnight. This material was the
catalyst precursor, which was crushed to fine powder and subsequently the catalyst
was produced by calcinations in the presence of air at 873 K for 4 hr [1,3]. Analytic
grade nickel nitrate, aluminum nitrate, cerium nitrate, zirconyl nitrate were used as a
catalyst precursor, support and promoter in the reforming reaction.
2.2. Catalyst activity
The CO2 reforming of methane was carried out at 923-1073 K and atmospheric
pressure, using 1 gm catalyst in a stainless steel tubular fixed-bed reactor. Fixed bed
reactor having tube of 18.05 mm inner, 19.05 mm outer diameter and tube length 500
mm.
Activation of the Ni-Catalyst involved reductive treatment with hydrogen at 773
K for 2 h with heating rate of 10 deg per min. The reactant feed gas was passed in
composition of CH4:CO2:N2 – 1:1:1 with total flow rate of 500 ml/min having GHSV
of 30000 cm3
/g*h.
The exit gases were analysed with gas chromatography equipped with thermal
conductivity detector with Porapak – Q and a SA molecular sieve column was used
[7]. In this work, conversions of methane and carbon dioxide and yields of hydrogen
and carbon monoxide were calculated according to the following formulas.
XCH4% = [CCH4in-CCH4out]/ CCH4in * 100
XCO2% = [CCO2in-CCO2out]/ CCO2in * 100
YH2% = CH2out/2CCH4in*100
YCO% = CCOout/[CCH4in+CCO2in] * 100

Where Xi and Yi are the conversion of reactants and yields of products,
respectively Ciin is the initial molar fraction of component i in the feed, and Ciout is the
final molar fraction of component i in the product stream [10].
3. CATALYST CHARACTERIZATION
3.1. XRD
The X-ray diffraction (XRD) patterns are studied in order to monitor not only the
catalyst structure but also the studied for the identification of the crystalline phase,
Model: X’PERT MPD, Make: Philips, Holland was used.
Information on crystallographic structure, chemical composition and physical
properties of materials and then films; x-ray scattering technique is used. XRD is a
part of non destructive analytical techniques [10].
These techniques are based on observing the scattered intensity of on x-ray beam
hitting a sample as a function of incident and scattered angle, Polarization and
wavelength or energy [12].
3.2. Physisorption Analysis
For determining the surface area and pore size distribution of solids, measurement of
gas adsorption isotherms are widely used. The identification types of isotherm are
required for interpretation of physisorption isotherm. This in turn allows for the
possibility to choose an appropriate procedure for evaluation of the textural
properties.
Non-specific Brunauer-Emmett-Teller (BET) method is the most commonly used
standard procedure to measure surface areas, in spite of the over simplification of the
model on which the theory is based. The BET equation is applicable at low p/po range
and it is written in the linear form: [11]
Sample pressure is p,
Saturation vapour pressure is po,
The amount of gas adsorbed at the relative pressure p/po, : na
The monolayer capacity, and C is the so-called BET constant: na
m
The adsorption-desorption data to be use for to assess the micro-and mesoporosity
and to compute pore size distribution, through number of way has been developed.
These are number of assumptions, e.g. relating to pore shape and mechanism of pore
filling for same.
3.3. Fourier Transforms Infrared Spectroscopy (FTIR)
FTIR spectroscopy gives information on interaction of absorbed molecules, yielding
information on [4, 5]
1) The site of interaction, i.e the active centers,
2) The restriction of molecular motion in the adsorbed state.
3) The geometry of the sorption complex and
4) The change of internal bonding due to adsorption.
To obtain an infrared spectrum of absorption, emission, photoconductivity or
raman scattering of a solid, liquid or gas fourier transform infrared spectroscopy is a

technique used. Over a wide spectral range FTIR spectrometer simultaneously
collects high spectral resolution data. This confers a significant advantage over a
dispersive spectrometer which measures intensity over a narrow range of wavelengths
at a time [5].
4. RESULTS AND DISCUSSION
4.1. X-Ray Diffraction of 5%Ni/5%CeO2-Al2O3 and 10%Ni/5%MgO-
Al2O3
The XRD patterns for Al2O3 supported, prepared by co-precipitation, 5%Ni, and with
different promoters (CeO2 and MgO) are shown in Fig. 1 and 2. The Al2O3, Ni, NiO,
CeO2, MgO, NiAl2O4 and MgAl2O4 phases were detected in the XRD patterns. By
increase of nickel loading the ratio of NiO intensity to Al2O3 intensity was improved.
In fresh catalyst the spectra corresponding to Ni was observed even at low Ni loading.
Second, peak depends on other situation like (a) most probable case of low Nickel
loading on the catalyst or (b) Formation of the NiAl2O4 phase [9].
According to the JCPDS files, the Al2O3, Ni, NiO, CeO2, MgO, NiAl2O4 and
MgAl2O4 phases can be detected in the XRD patterns [15]. NiO diffraction peaks
observed at 2 37.3, 43.4, 44.5, 62.9, 63.0, 75.6 and 79.6. Characteristic
diffraction peaks of phases at 2 of 19.2, 31.6, 45.3, 56.4, 60.0, 66.2 and 2 of 19.1,
31.4, 37, 45, 59.7, and 65.5 are assigning to MgAl2O4 and NiAl2O4 respectively [7-9].
The smaller amount of Ni interact with alumina and form nickel aluminate (NiAl2O4)
composite layer, which is an amorphous phase or a crystalline phase with crystallite
sizes smaller than the detection limit of XRD. Basically a crystallite size of NiAl2O4
is smaller than the recognition limit of XRD.
Figure 1 X-Ray diffraction pattern of the catalyst 10%Ni/5%CeO2-Al2O3
In Fig. 1, the XRD patterns of 10Ni/5%CeO2-Al2O3 shows intense diffraction
lines of NiO (2θ= 43.2°), Al2O3 (2θ = 66.3°) and CeO2 (2θ = 29°, 57°). In this catalyst
single major phases of alumina and crystalline phase of nickel and two of phases of
CeO2 were detected. The amount of CeO2 addition influenced the intensities of

Nickel peaks. The weaker and broader the Ni Peak due to the more CeO2 loading on
catalyst. It indicates that addition of CeO2 effects the nickel dispersion on catalyst.
Figure 2 X-Ray diffraction pattern of the catalyst 10%Ni/5%MgO-Al2O3
The overlap of alumina and nickel oxide form composite layer of NiO-Al2O3
which is an amorphous phase. The smaller amount of Ni particle interacts with
alumina and form nickel aluminate (NiAl2O4). It is clear that strong interaction of
nickel metal and alumina lattice to make spinel type solid solution of NiAl2O4. There
is NiAl2O4; the strong interaction is due to the calcination. The presence of Ni in the
form of NiO can be observed in XRD patterns as well. The NiO crystallites are small
and well dispersed in catalysts samples as the related peak are quire broad. It should
be mentioned that NiO crystals are slightly bigger in the presence of CeO2 and in
contrary, alumina peaks lost their intensity after introduction of CeO2. According to
XRD patterns, big crystal of CeO2 was observed.
In Fig. 2, the XRD patterns of 10%Ni/5%MgO-Al2O3 shows intense diffraction
lines of NiO (2θ= 62.7°), Al2O3 (2θ = 42.8°) and MgO (2θ = 74.8°, 78.7°). As Ni2+
,
Mg2+
, Al3+
, fall in to the same lattice, the formation of solid solution of spinel type of
MgAl2O4 and NiAl2O4 is favored under high temperature calcination. As Ni2+
, Mg2+
,
Al3+
, fall in to the same lattice, the formation of solid solution of spinel type of
MgAl2O4 and NiAl2O4 is favored under high temperature calcination.
4.2. BET Surface Area
The surface area, pore size and pore volume of the catalysts containing 5%, 10% Ni
by weight and promoted with CeO2 are presented in table 1.
Table 1 Physical properties of catalysts.
Catalyst BET Surface Area
(m2
/g)
Pore Volume
(cm3
/g)
Pore Diameter
(nm)
5%Ni/Al2O3 142.56 0.24 5.31
10%Ni/Al2O3 130.19 0.20 5.65
10%Ni/5%CeO2-Al2O3 105.21 0.18 6.10

It appears that catalyst surface area decrease with increased nickel loading from
5% to 10%. As more metal is precipitated, more of the pores originally present are
being filled up, this effectively reducing surface area.
4.3. FTIR Analysis
FTIR analysis is shown in Fig. 3 and 4. For a more precise IR characterization,
spectra were reported in a wide range of frequency 400-4000 cm-1
.
Figure 3 FTIR Spectra of 10%Ni/CeO2-Al2O3.
Figure 4 FTIR Spectra of 10%Ni/ZrO2-Al2O3.
The IR spectra in all cases, exhibit metal-oxygen stretching frequencies in the
range 470-900 cm-1
associated with the vibration of M-O, Al-O and M-O-Al bonds
(M=Ni, CeO2, and ZrO2). Peaks of stretching vibration of structured O-H at 3450
cm-1
, and stretching vibration at 1640 cm-1
is due to the physically adsorbed water and
clear form the spectrum of the catalysts.

The residual nitrate compounds present in the catalyst after heat treatment and
especially nitrogen used for the reaction is responsible for the appearance of N-O and
N-C peaks at 1525 cm-1
. The peaks at 415 cm-1
corresponds to the metal-oxygen –
metal band. This band can also be related to the stretching vibration absorption
spectrum of Ni. Absorption peaks of metal oxides (NiO, ZrO2, and CeO2) arising from
inter atomic vibrations are below 1000 cm-1
. An absorption peaks at 1400, 1649 and
3450 cm-1
are related to adsorbed water for all materials [14, 17].
Effect of Ni loadings with different promoters at different temperatures
In Fig. 05 & 06 shows the Ni loading on the activity of Ni/Al2O3 catalyst
presented in terms of feed conversion and product yields in Fig. 05, 06 and 07.
Figure 5 CH4 conversion (%) over different temperature (K) in Dry Reforming of methane.
As Ni loading increased up to 10% conversion of both CH4 and CO2 were
considerably increased. At low Ni-loading conversion of CH4 and CO2 were
observed low, due to the small active nickel metal and the formation of NiAl2O4 even
though their surface area is relatively high compared to 10%Ni loading.
When Zirconia added, both CH4 and CO2 conversions were strongly increased. It
is proposed that the presence of ZrO2 inhibits the NiAl2O4 formation. Further the
Al2O3 surface is changed due to ZrO2 and Ni is not placed straight onto the Al2O3 but
near to ZrO2, as a result CO2 dissociation increase. Similar results and explanations
were also found by Seo et al. [42], explaining that ZrO2 inhibits the inclusion of
nickel species into the lattice of Al2O3, preventing the growth of metallic nickel
particles during the reaction step.

Figure 6 CO2 conversion (%) over different temperature (K) in Dry Reforming of methane.
Figure 7 H2/CO Ratio over different temperature (K) in Dry Reforming of methane.
This causes gasification of the dissociated oxygen and unsaturated intermediates
and promotes the formation of carbon deposit precursors, prevents coke formation in
the system [5, 10]. Among all catalyst prepared by co-precipitation, the catalytic
activity of 10Ni/5%ZrO2-Al2O3 was high. Pompeo et al. also [11] explained the coke
reduction capability of ZrO2 similar to our results.
It is also noticeable that CeO2 promoted catalyst has superior CH4 conversion then
unsupported at all temperature. There are two main causes for same (1) CeO2 has higher
surface basicity compare to alumina and the formation of different types of carbonate
like species due to interaction of CeO2 with CO2. [18] (2) CeO2 has oxidative properties
and a good capacity for oxygen storage reaction [12]. With effect of CeO2; carbon
generated from CH4 dissociation and on catalyst; carbon atom reacted with oxygen-
containing species from the dissociation. Due to the faster reaction rate of carbon

species formed on Ni/CeO2-Al2O3 catalyst, these system exhibits higher activity than
Ni/Al2O3 catalyst. The converge of Ni metal by CeOx species induced by strong metal
surface interaction and the dispersive ability of CeO2 preventing the formation of large
metal ensembles reduced the carbon deposition on Ni/ CeO2-Al2O3.
It is worth noting that, excellent performance of MgO in raising of basic sites
concentrations and consequently, promoting the adsorption rate of acidic CO2 [13]. In
presence of MgO, there is formation of MgAl2O4 phase and surface rearrangement
lead to improvement in catalytic activity [14].
Xu et al [43]. reported that NiO-MgO-Al2O3 catalyst was displaying high catalytic
activity and long catalytic stability. Monica Garcia-Dieguze et al [44]. expressed that
the Mg incorporation to Ni/Al2O3 catalysts improves the Ni dispersion by surface
rearrangement and further reduces the carbon formation. The magnesium aluminate
support has been used for steam reforming of hydrocarbons due to its having high
sintering resistance ability. It is prominent support for nickel catalysts, as due to its
high sintering resistance ability and low acidity stability [15]. Helvio Silvester A.
Sousa et al [45]. reported that better catalytic performance was found in case of Ni-
containing MgAl2O4 and NiAl2O4 phase due to the increased resistance against
physical degradation, but coking was found to decrease activity.
4.5. Effect of temperature
For all co-precipitated catalyst the consequence of temperature on the conversion of
reactant and product gas (H2 and CO) yields are given in Fig. 05 to 07. DRM is
highly endothermic reaction as temperature increased conversion of CH4 and CO2 is
increased and also the yields of H2 and CO [21].
Over all the catalyst and all examined temperatures, the conversions of CO2 were
higher than those of CH4 which can be due to the existence of RWGS (reaction 2)
reaction. Highest 76.55% and 80.13% conversion of CH4 and CO2 achieved at 1073 K
respectively with 10%Ni loading with effect of ZrO2. The RWGS is also contributed
to higher CO2 conversion then CH4 conversion at low temperature, as reported [17].
CH4 dissociation is also increased and greatly enhanced at higher temperatures. It
leads to formation of coke, as conversion of methane is increased. In sort at higher
temperature the CH4 dissociation is a strongly favoured reaction. The increase of CH4
dissociation is demonstrated not only in terms of feed conversion but also the coke
yield. This suggests that the CH4 decomposition dominates the CO2
disproportionation for the coke formation at high temperatures, as was
thermodynamically calculated by S. Therdhianwong et al [18]. Increase in H2/CO
ratio was detected when temperature raised, though in all cases ratio was below unity,
it indicates that RWGS was always taking place but in lower extent when the
temperature increased. Further, most of Ni crystallites remain and partially form NiO
with oxygen species dissociated form CO2 at higher temperature.
4.6. Effect of GHSV
Results in Fig. 8 & 9 show the influence of space velocity on catalytic activity for the
reaction conversion and H2/CO ratio. The space velocity is varied by changing the
total flow rate maintains at molar feed ratio of one and catalyst amount of 1 g.
Moreover, the CH4 and CO2 reforming reaction were conducted at constant
temperature of 1073 K. By increasing GHSV form 30000 to 48000 cm3
/g*h both CH4
and CO2 conversion decrease. As the space velocity increase, yields of H2 and CO
decrease.

For DRM reaction low velocity is suitable for better conversion and product yield.
For reaction it is required to interaction between reactant and active Ni particles inside
the catalyst pores, in case of high GHSV, the residence time is limiting factor for
reaction. In such situation number of reactant remain un-reacted. Number of
technical theory was made for above interpretation.
At higher GHSV there is external diffusion resistance that lead reduction in both
CH4 and CO2 conversion, similar to observation of Mark and Maier [20]. According
to our results, an increase in GHSV has converse outcome for CH4 and CO2
conversion over all sample catalysts high GHSV means lead to a lesser amount of
contact time, so reactant does not have sufficient time to penetrate in catalyst pores. In
other word, limitation is mass transport at higher GHSV. As shown in Fig. 9 the H2
and CO yields decreases as GHSV increases for all catalyst.
Figure 8 CH4 (%) and CO2 (%) conversion over different GHSV (cm3
/g*h).
Figure 9 H2/CO ratio over different GHSV cm3
/g*h

4.7. Stability test
Improvement and development of low cost catalyst with high activity alongside
excellent stability can be properties of a commercial catalyst for DRM. Fig. 10 & 11
gives the methane and carbon dioxide conversion at different time on stream over the
three promoted catalysts prepared by co-precipitated method. All of the co-
precipitated catalyst samples illustrated the reasonable stability and acceptable
performance during reaction time. There is deactivation in all three catalysts upto
certain extent. The stability improvement can be anticipated by the ratios between the
CH4 and CO2 conversion after 12 h (720 min) of time on stream (C12=C1) ratios were
0.78, 0.73, 0.74 for 10Ni%/5%CeO2-Al2O3, 10Ni%/5%ZrO2-Al2O3 and
10Ni%/5%MgO-Al2O3 respectively.
Figure 10 Comparison of stability test of different catalyst over time (h) in terms of CH4
conversion (%)
Figure 11 Comparison of stability test of different catalyst over time (h) in terms of CO2
conversion (%)

The stability was better over the CeO2 promoted catalyst compared to other
promoted catalysts. It was clear from results that good stability of the 10%Ni/CeO2-
Al2O3 catalyst compared to ZrO2 and MgO promoted catalyst. ZrO2 and MgO
promoted catalysts indicate reducing trend in conversion of reactant and product
yield. The rate of the atomic carbon gasification by CO2 is limited than the rate of
atomic carbon formation, and carbon will be polymerized [1, 21], is the major reason
for deactivation and it lead to coke formation. If deposited carbon having filamentous
structure then it’s does not deactivate the nickel sites. In reaction performance,
reactant accessible to active metals carried on the top, and as a result the activity
remains constant. These polymerized carbon atoms can deactivate Ni particle via two
ways: (a) encapsulating carbon or diffusing through the Ni after dissolving and (b)
detaching Ni particles from the support. In order to authenticate of this witnessing a
look over the mechanism of DRM might be useful. It is indicated that the CH4
decomposition occurs on the surface of the active metals while CO2 adsorption take
place on the support. Adsorbed CO2 reacts with carbon species derived from
dissociative adsorption of CH4. Therefore, CO releases and deposited carbon
removes. As a result of smaller particle size and enhanced dispersion, higher surface
area obtained and subsequently the rate of the carbon removal promotes.
It is the case in which nickel sites does not deactivate by deposited carbon. For
any reaction and in terms of activity, active metal should be straight forwardly
approachable to the reactants. The active metal is carried on the top of the carbon
filament and, as a consequence, the catalytic activity remains constant since the active
metal is still accessible to the reactants. The stability was better with effect of MgO
compare to ZrO2 catalyst. Higher stability with MgO promoted catalyst was due to
proper interaction among Ni and support, which results uniform dispersion of Ni
particles, resistance to carbon deposition and sintering [22]. Bond between metal and
support is strong, structure remains strong and if bond is not strong, structure remains
weak, and then carbon formation via methane decomposition is more probable.
Excellent stability of the catalyst can be ascribed to the uniform particle size
distribution and to strong metal support interaction (SMSI) effect.
5. CONCLUSION
The desirable catalyst with high specific surface area, uniform particle size
distribution, high dispersion of active metal and strong metal surface interaction
effect, is the most considerable efforts for DRM commercialization. Ni catalyst
supported over alumina and different promoters like CeO2, ZrO2 and MgO were used
for DRM. From our study, few conclusions can be drawn as below.
According to results of characterization techniques and reactivity tests for
promoted and un-promoted catalyst, prepared by co-precipitation method:
1. The optimum Ni (10%) loading gives higher conversion, it is due to small and well
dispersed NiO crystals. The 10%Ni/5%ZrO2-Al2O3 co-precipitated catalyst gives
higher activity compare to other promoted and un-promoted catalysts prepared by
same method. The 10%Ni/5%ZrO2-Al2O3 catalyst displayed high catalytic
performance for CO2/CH4 reforming at 1073K because the small size of nickel
particles maintained enough active sites on the surface of catalyst. 10%Ni/5%ZrO2-
Al2O3 catalyst gives higher H2/CO ratio compare to other two promoted catalyst and
near to unity.
2. It has been observed that by increasing reaction temperature the percentage
conversion of methane increase as DRM is endothermic. The present investigation

confirms that at high GHSV the conversion of CH4 and CO2 in declined trend, as
reactant does not have sufficient time to react over the surface of Ni.
3. In DRM reaction coke deposition over catalyst due to RWGS reaction and the
dissociation of CH4. Promoters (CeO2, ZrO2 and MgO) were used to avoid and
control deactivation. The effect of CeO2, ZrO2 and MgO addition to Ni/Al2O3 catalyst
were studied to enhanced activity and stability of the prepared catalyst for dry
reforming of methane. Deactivation was observed with all Ni catalyst supported on
Al2O3 and promoted CeO2, ZrO2 and MgO up to some extent. CeO2 promoted catalyst
exhibits comparatively constant recitation for 12 h on stream.
4. XRD measurement also indicates the introduction of CeO2 enhances the dispersion of
nickel particles and reducibility of Ni/Al2O3 also increased and inhibited the
formation of NiAl2O4. Addition of CeO2 in to 10%Ni/Al2O3 system does not also
suppressed the carbon deposition, because CeO2 enhanced the Ni dispersion and
reactivates of carbon deposition.
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