High Temperature Co2 Reactions

REVIEW ARTICLE
ENERGY RESEARCH
published: 18 March 2015
doi: 10.3389/fenrg.2015.00013
CO2 as an oxidant for high-temperature reactions

Sibudjing Kawi * and Yasotha Kathiraser
Department of Chemical and Biomolecular Engineering, Faculty of Engineering, National University of Singapore, Singapore, Singapore
Edited by: This paper presents a review on the developments in catalyst technology for the reactions
Camille Petit, Imperial College
utilizing CO2 for high-temperature applications. These include dehydrogenation of alka-
London, UK
nes to olefins, the dehydrogenation of ethylbenzene to styrene, and finally CO2 reforming
Reviewed by:
Victor Vilarrasa, Lawrence Berkeley of hydrocarbon feedstock (i.e., methane) and alcohols. Aspects on the various reaction
National Laboratory, USA pathways are also highlighted. The literature on the role of promoters and catalyst devel-
Robert J. Farrauto, Columbia opment is critically evaluated. Most of the reactions discussed in this review are exploited
University in the City of New York,
in industries and related to on-going processes, thus providing extensive data from litera-
USA
ture. However, some reactions, such as CO2 reforming of ethanol and glycerol, which have
*Correspondence:
Sibudjing Kawi , Department of not reached industrial scale, are also reviewed owing to their great potential in terms of
Chemical and Biomolecular sustainability, which is essential as energy for the future. This review further illustrates the
Engineering, Faculty of Engineering, building-up of knowledge that shows the role of support and catalysts for each reaction and
National University of Singapore, 4
the underlying linkage between certain catalysts, which can be adapted for the multiple
Engineering Drive 4, 117576
Singapore CO2 -related reactions.
e-mail: [email protected]
Keywords: CO2 utilization, reforming, dehydrogenation, catalyst, hydrocarbon
INTRODUCTION of this review is to focus on the utilization of CO2 as an oxidant

Rising levels of CO2 in atmosphere caused severe impacts, such as for alkane dehydrogenation as well as reforming of hydrocarbons
the increasing intensities of hurricanes, influence of El Nino phe- to synthesis gas, which is the building block for chemical synthesis.
nomena, reduced calcification of marine plankton, and deglacia- According to Bartholomew (1984), the oxidizing ability of var-
tion (Wu and Kawi, 2009). It is clear that it is important to stabilize ious gases in carbon gasification is in the order of O2 (105) > H2 O
CO2 levels to prevent escalation, but it is even more ideal to reduce (3) > CO2 (1) > H2 (0.003). Among these gases, O2 is widely used
CO2 concentrations in order to avoid catastrophic and irreversible for oxidative dehydrogenation (ODH) reactions, whereas water in
environmental damage (Styring and Armstrong, 2011). Presently, the form of steam is used for reforming of hydrocarbon/alcohol
a major practice of abating CO2 emission involves capture and reactions.
storage technologies whereby CO2 will remain in supercritical
conditions during storage (Styring and Armstrong, 2011). Never- OXIDATIVE DEHYDROGENATION OF ALKANES
theless, the transportation of CO2 through pipelines is carried out CO2 utilization in the ODH of alkanes has received significant
under liquid conditions (McCoy and Rubin, 2008) and injection attention in recent years. By co-feeding CO2 in the ODH of light
of CO2 is carried out in liquid form as well (Vilarrasa et al., 2013); alkanes, as a “soft oxidant,” the reaction equilibrium is shifted
therefore, from this aspect there is no safety issue. This, however, toward more olefin production (Urlan et al., 2008; Raju et al.,
overlooks the fact that, besides depletion of storage space, for every 2014). The ODH reaction is interesting as it can directly produce
molecule of CO2 stored; there is one less carbon atom participa- olefins, such as ethylene, propylene, and butylenes, from their
tion in the carbon economy. Chemical utilization of CO2 , being respective alkane sources. These olefins are known to be build-
one of the major greenhouse gases, is an important step toward a ing blocks in the petrochemical industry. For example, ethylene is
mature technology that contributes to C–C cycling and reduction widely used for the production of plastics, polymers, fibers, and
in CO2 concentrations, as well as toward economic, renewable, packaging materials (Qiao et al., 2014). The industrial synthe-
and environmental synthesis of value added product (Ansari and sis of ethylene via steam cracking of hydrocarbons or naphtha is
Park, 2012; Aresta et al., 2013). very energy consuming, and the catalysts are afflicted by coking
One of the major concerns regarding CO2 chemical utilization resulting in catalyst deactivation (Qiao et al., 2014). Therefore, it is
is related to the thermodynamic stability of the CO2 molecule. more desirable to utilize an oxidant capable of mildly oxidizing the
Additional energy and co-reactants are required for full conver- reaction environment in order to inhibit the coking phenomenon.
sion of the CO2 molecule into value-added products. However, Usage of molecular oxygen as oxidant can effectively reduce the
recent improvement in efficiency of sustainable energy supplies, reaction temperature and inhibit coking, however, issues such as
such as solar and geothermal, enhances the economical viabil- low selectivity due to the production of COx species from HCs and
ity of CO2 utilization. One of the technologies that are gaining the need to remove excess heat of reaction prevail (Rangel et al.,
prominence is the utilization of CO2 as an oxidant for catalytic 2012). However, CO2 has been found to serve as a suitable medium
transformations under dehydrogenation as well as reforming reac- for heat supply for the endothermic dehydrogenation reaction and
tions under high-temperature environments. The main highlight as a coke removal agent from the catalyst (Urlan et al., 2008). In
www.frontiersin.org March 2015 | Volume 3 | Article 13 | 1

Kawi and Kathiraser CO2 as an oxidant for high-temperature reactions
addition, CO2 improves olefin selectivity compared to molecular of their high catalytic activity, reduction of the active chromium
O2 by preventing deep oxidation of the reaction products, thus species led to catalyst deactivation. According to Takehira et al.
improving the olefin selectivity (Liu et al., 2011). (2004), based on EXAFS data, the coordinatively unsaturated
The general reaction pathway for the CO2 -ODH is shown in tetrahedral Cr(VI) represents the active site for alkane dehydro-
Eq. 2.1: genation; whereas the coordinatively saturated bulk Cr(III) ions
are less active for alkane dehydrogenation (Cavani et al., 1996;
Cn Hn+2 + CO2 → Cn Hn + CO + H2 O (2.1) Liu et al., 2007). CO2 plays an important role in regenerating the
deactivated catalyst. Similar to mesoporous-based supports, the
It should be noted that the olefins produced from dehydrogena- catalytic activity of chromium supported on silica was found to
tion of higher alkanes, contain allylic hydrogens, which are coke depend on the chromium dispersion (Botavina et al., 2008). Based
precursors, being the main cause of catalyst deactivation, which on the study by Botavina et al. (2008), DR-UV–vis studies indicate
in turn leads to low olefin yields. Thus, optimization of catalyst that surface chromates with lower nuclearity possess high activity
systems is of paramount importance for this process. On the other compared to Cr(VI) in the form of extended polychromates (less
hand, the CO and H2 O by-products can be reacted together for the dispersed).
production of hydrogen via the low-temperature water gas shift Besides supporting catalysts on the mesoporous supports, it
reaction. However, pure CO, by itself has many uses in the chem- is also possible to incorporate the catalyst within mesoporous
ical industry especially as a secondary feedstock for production structures. For example, Liu and Li (2006) synthesized Cr incor-
of acetic acid by methanol carbonylation process, production of porated into MSU-1 (a type of mesoporous molecular sieve) and
phosgene, formic acid, etc. Cr supported on MSU-1, the former labeled as Cr-MSU-1 and
The patented processes for ODH of hydrocarbons are usually the latter as Cr/MSU-1 for CO2 -ODH of ethane. They found that
based on the concept of utilizing oxidants, such as O2 , CO2 and despite higher activity for the Cr supported catalysts, especially at
SO2 , coupled with steam in order to shift the equilibrium of the Cr loading >1 wt%, however, it also resulted in lower selectivity
dehydrogenation reaction toward enhanced conversion. Steam was due to cracking reactions caused by a higher ratio of inactive poly-
used to activate the catalyst as well as function as a coke removal chromate species. Furthermore, the catalyst dispersion at higher
agent via the water gas shift reaction in an invention described by than 8 wt% loading is severely affected resulting in the decrease of
Budin and Meyer (2003). More recently, Smith (2008) described Cr(VI) species and increase in crystallite Cr2 O3 species (Liu et al.,
a process in which ethane and ethylbenzene are simultaneously 2007). Recently, Baek et al. (2012) synthesized highly dispersed
dehydrogenated in the presence of CO2 or steam at tempera- chromium oxide catalysts supported on mesoporous silica using
tures ranging between 500 and 700°C in the presence of catalysts an electrostatically controlled assembly process. A high (90%)
comprising transition metals (V, Cr, Mn, Fe, Co, Ni, etc.) and selectivity toward propylene formation was achieved with a yield
supported on high surface area supports. This method results in of 30% in the CO2 -ODH of propane. Within 25 h, propane con-
the production of a mixed product feed stream comprising ethyl- version reached steady state and the deactivation observed was
ene, styrene, ethylbenzene, ethane, hydrogen, water, CO, and CO2 , related to coke formation and reduction of active chromium sites.
whereby the ethane and ethylene product stream can be recycled CO2 as oxidant (Scheme 1) enhances regeneration of the
in other processes, which include alkylation of benzene or other reduced chromium sites formed during the dehydrogenation of
polymerization processes. propane (Eq. 2.2) and the successive reduction with H2 (Eq. 2.3)
(Michorczyk et al., 2012), where CrOx represents the oxidized form
CATALYTIC SYSTEMS FOR CO2 -ODH OF ALKANES and CrOx-1 represents the reduced form of the catalyst). Based
It should be noted that catalysts with redox properties, such as on Scheme 1, the by-products of this reaction are CO and H2 O,
molybdenum-, chromium- and vanadia-based catalysts, possess whereby CO can easily react with H2 O producing valuable hydro-
high catalytic activity for the various ODH reactions of hydrocar- gen via the water gas shift reaction:
bons (Solymosi et al., 2001; Michorczyk et al., 2012). The main -------------------------------------------------
factors influencing the reaction include acid–base bifunctionality,
which is important in CO2 -mediated dehydrogenation reactions C3 H8 + CrOx ↔ CrOx−1 + C3 H6 + H2 O (2.2)
since both basic sites and Lewis-acid vacant sites play important CO2 + CrOx−1 ↔ CO + CrOx (2.3)
functions in hydrocarbons activation (Deng et al., 2007; Pramod H2 + CrOx ↔ CrOx−1 + H2 O (2.4)
et al., 2014).
Investigations on chromium-based catalysts supported on CO2 + CrOx−1 ↔ CO + CrOx (2.5)
mixed oxides, mesoporous silica, and zeolites (Zhang et al., 2002;
SCHEME 1 | CO2 -ODH of propane to propylene over chromium
Takehira et al., 2004; Zhao and Wang, 2006) have been carried
oxide catalytic sites.
out for CO2 -ODH (Nakagawa et al., 2003). These supports pos-
-------------------------------------------------
sess high surface area that ensures good catalyst dispersion, which
is essential for high catalytic activity and stability. Cr-based cat- The consequence of promoters, such as Fe, Co, and Mn oxides,
alysts supported on zeolitic TS-1 (Zhang et al., 2002), high silica on Cr-based Cr2 O3 /ZrO2 nano-composite catalysts for CO2 -ODH
H-ZSM-5 (Mimura et al., 2006), and siliceous MCM-41 (Takehira of ethane was found to distinctly enhance ethylene selectivity
et al., 2004) were shown to exhibit good activity and selectivity for (Deng et al., 2007). It was observed that weak acid sites promote the
the CO2 -ODH reaction of ethane and propane. However, in spite ethylene formation through improved ethane activation, whereas
Frontiers in Energy Research | Carbon Capture, Storage, and Utilization March 2015 | Volume 3 | Article 13 | 2
strong acid–base sites favor the undesired reactions of reforming Urlan et al. (2008) reported that the ODH of n-butane over
and ethane cracking (Deng et al., 2007). In addition, the oxy- titanium pyrophosphate (TiP2 O7 ) can be enhanced by co-feeding
gen species types, i.e., the lattice oxygen (OI ), oxygen in adsorbed CO2 in the system. However, feeding CO2 only caused lower con-
CO2 or carbonates (OII ), and adsorbed oxygen species (OIII ), can versions. Similarly, increasing CO2 partial pressures over V–Mg–O
influence the reaction rate and ethylene selectivity. Lattice oxygen catalysts improved yield and selectivity of C4 dehydrogenation
species are responsible for selective oxidation of hydrocarbons, products (Ge et al., 2003).
whereas the adsorbed oxygen species result in more COx forma- The molybdenum oxide-based catalysts possess a chemistry
tion due to deep oxidation (Pena and Fierro, 2001; Deng et al., comparable to that of vanadium oxide, due to the fact that Mo can
2007). Catalysts, such as Na2 WO4 /Mn/SiO2 , suitable for oxida- be present as MoOx monomers, polymers, or MoO3 crystallites.
tive coupling of methane reaction are also active in the ODH of The various forms of Mo depend on the loading, support type, and
ethane (Pak et al., 1998). In fact, Han et al. (2010) patented a mixed catalyst preparation methods (Sattler et al., 2014). For example, in
valent catalyst system comprising synthetic cryptomelane or octa- a Mo2 C/SiO2 system, by co-feeding CO2 for the ODH reaction, the
hedral molecular sieve with Fe as the transition metal for the CO2 benefits of CO2 in oxidizing the Mo2 C forming Mo-oxycarbide at
dehydrogenation of ethane at 550°C in order to produce ethylene higher temperatures could be observed (Solymosi and Nemeth,
and CO mixtures, which are used as feedstock for the ethylene 1999; Solymosi et al., 2001). In fact, Dury et al., 2003a) reported
homologation to propionic acid derivatives. that dissociation of CO2 on the catalyst surface could take place
The catalytic properties of vanadium oxide correlate to the due to introduction of 3% CO2 for the ODH reaction of propane
supports’ acid–base nature (Blasco et al., 1995) as well as on the over NiMoO4 hence inducing the oxidation of molybdenum sub-
vanadium dispersion on the support (Liu et al., 2004). Raju et al. oxide at temperatures around 673–723 K. The presence of both
(2012) synthesized V2 O5 supported on various mixed oxides, such molybdates and molybdenum oxides can enhance the catalytic
as SnO2 –ZrO2 , CeO2 –ZrO2 , and TiO2 –ZrO2 (Raju et al., 2014). properties of NiMoO4 in hydrocarbon oxidation (Lezla et al., 1997;
The high surface area and superior acid–base bifunctionality of Dury et al., 2003a). CO2 dissociation results in formation of oxy-
SnO2 –ZrO2 supported V-catalyst were found to demonstrate good gen species that have higher selectivity compared to molecular
catalytic activity compared to vanadia supported on single oxides. oxygen and radical formation can be avoided.
The nature of the support strongly affects reducibility of V2 O5 .
However, in the case of CeO2 –ZrO2 supported V2 O5 , despite OXIDATIVE DEHYDROGENATION OF ETHYLBENZENE TO
the slightly lower conversion caused by TiO2 –ZrO2 and SnO2 – STYRENE
ZrO2 supported catalysts, the total selectivity toward butylene is The ODH of ethylbenzene (ODE) to styrene reaction is grow-
much higher with the main reason being participation of larger ing rapidly as a promising alternative to the current steam-based
amounts of lattice oxygen species and oxygen vacancies (which are process in view of the increasing demand of styrene and its rapid
replenished by CO2 ) forming CeVO4 species (Raju et al., 2014). market growth (Castro et al., 2013). Styrene is an important pre-
Evidently this is due to the redox nature of CeO2 –ZrO2 supports cursor for high-value commercial products such as synthetic rub-
that increases oxygen mobility and facilitates oxidation/reduction bers, polystyrene, and styrene–acrylonitrile copolymers (Ba et al.,
of the Ce4+ /Ce3+ couple (de Lima et al., 2008; Postole et al., 2010). 2014). Industrially, excess of steam is required for ethylbenzene
Mesoporous structured supports, such as MCM-41 or SBA- dehydrogenation to styrene to overcome both carbon deposition
15, are highly favorable to improve catalyst dispersion. As such and reaction thermodynamics (Jiang et al., 2009; Pramod et al.,
impregnation of vanadium on mesoporous siliceous MCM-41 was 2014). However, being a highly endothermic process, the conver-
found to result in greater density of surface-active sites owing to sion rarely exceeds 50%. Furthermore, the production of toluene,
large pore diameters and the stronger interaction, which exists benzene, and coke, due to side reactions, also affects the process
between the active species and its support compared to amor- yield and selectivity, and leads to catalyst deactivation (Rangel
phous silica (Solsona et al., 2001). Furthermore, the thicker walls et al., 2012). As aforementioned, the deep oxidation and radical
(31–64 Å) of SBA-15 types of mesoporous silica compared to their formation associated with oxygen as the dehydrogenation agent
MCM-41 counterparts lead to greater thermal and hydrothermal led to growing use of CO2 as dehydrogenating agent, in order to
stability (Liu et al., 2004). Isolated tetrahedral vanadium oxide enhance styrene selectivity (97%) and prevent hot spots (de Araujo
species containing terminal V=O groups well dispersed on the et al., 2010; Irún et al., 2013). Via the use of CO2 , the explosion risks
mesoporous silica at predominantly low vanadia content (in order associated with use of oxygen can be mitigated besides ensuring
to prevent polymerization) have been identified to be the active high selectivity toward styrene production (Park et al., 2005).
sites. Park et al. (2005) in their invention described the process of
Early studies for ODH of alkanes were focused on co-feeding utilizing CO2 as a soft oxidant for the dehydrogenation of alky-
CO2 as a promoter along with O2 in order to improve the dynamic laromatic hydrocarbons, such as ethylbenzene, in the presence of
phenomena at the surface of oxides resulting in greater olefin heterogeneous catalysts containing vanadium and iron in various
yields. Thus in these works, CO2 acted as a modulator of the configurations. As compared to the conventional processes, utiliza-
oxidative properties of oxygen (Dury et al., 2003a; Park and Ansari, tion of CO2 as a“soft oxidant”enables operation at a lower temper-
2013). Among the advantages of CO2 introduction in the system ature and provides significant energy savings along with improved
are lower tendency for hydrocarbons combustion (whilst mini- conversion (Park et al., 2005). In fact, the energy consumption for
mizing hot spot formation) and decrease in coking effect (Dury the CO2 -based ODE process compared to steam-based is about
et al., 2003b). 1.5–1.9 × 105 instead of 1.5 × 106 kcal/mol of styrene produced

(Rangel et al., 2012). In a more recent invention described by CATALYTIC SYSTEMS FOR CO2 -ODE TO STYRENE
Schwint and Wilcox (2009), the process information is described Redox nature and acid–base properties of the catalyst are several
in detail. In summary, the CO2 required for the dehydrogenation of factors, which are important to improve selectivity toward styrene
ethylbenzene to styrene monomer can be supplied externally from production. Early research showed that iron catalysts on various
the release of another petrochemical process as a recycle stream. supports, such as alumina and activated carbon, are promising for
The process steps include details on addition of steam, hydrogen, enhanced styrene selectivity in the CO2 -mediated ODE reaction
methane, or other hydrocarbon fuel to the recycle carbon diox- (Badstube et al., 1998; Mimura and Saito, 2000). However, the
ide stream. The CO2 and ethylbenzene stream is heated in a heat existence of some disadvantages, such as low-surface area and sus-
exchanger and fed to an oxidizer having a selective oxidation cat- ceptibility toward deactivation of the catalytically active Fe3+ sites,
alyst. Two-stage oxidizer and two-stage dehydrogenation reactors propelled the need for promoters, such as titania (de Araujo et al.,
coupled with heat exchangers are used for the conversion of ethyl- 2010; Castro et al., 2013). For example, among the promoters, such
benzene to styrene. With the presence of CO2 in the feed stream, as Ti, Al, and Zr, Ti modification showed much promise (Castro
the superheated steam used for the heat exchangers is required in et al., 2013). Formation of FeTiO3 , Fe2 TiO5 , and FeTi2 O5 stable
lower quantities than conventional ethylbenzene dehydrogenation mixed oxide phases improved resistant against phase transforma-
processes. A distillation column is used to separate the dehydro- tion and sintering and, thus, assuring high catalytic performance.
genation product mixture from the styrene monomer (Schwint However, styrene oligomerization occurred while the formation of
and Wilcox, 2009). carbon was increased due to ethylbenzene cracking (Castro et al.,
Based on Scheme 2, the overall process is shown in Eq. 3.1, 2013).
whereas the two-step pathway is presented in Eqs 3.2 and 3.3 as Iron oxide doping on ceria-based catalysts can result in forma-
follows (Mimura and Saito, 2000): tion of Ce1–x Fex O2 solid solutions, which performed better than
ceria-based Zr, Ti, Pr, and Y mixed oxides (Wang et al., 2014a). The
------------------------------------------------- Ce1–x Fex O2 solid solutions were synthesized via the hydrothermal
method resulting in a highly dispersed Fe2 O3 on the surface of
C6 H5 CH2 CH3 + CO2 → C6 H5 CH = CH2 + H2 O + CO (3.1) the Ce stabilized structure (Wang et al., 2014a). Raman analysis
C6 H5 CH2 CH3 → C6 H5 CH = CH2 + H2 (3.2) was used to confirm the solid solution formation with Fe3+ in the
CeO2 lattice. Even though Fe3+ doping can potentially improve
H2 + CO2 → CO + H2 O (3.3)
the reaction kinetics (Wang et al., 2014a), however, it has a lower
energy for the formation of oxygen vacancies, compared to the
SCHEME 2 | Pathway schematic for CO2-ODE to styrene.
un-doped system. These oxygen vacancies are crucial in promot-
-------------------------------------------------
ing rapid oxygen exchange between Ce4+ and Ce3+ redox sites
Based on Eq. 3.3, the produced hydrogen from the dehy- (improving oxygen storage capacity of ceria), thus enabling iron
drogenation step is removed as steam by the reverse water gas to maintain its high shift activity promoting. In addition, CO2
shift (RWGS) reaction to further shift reaction equilibrium. The adsorption and activation were enhanced leading to a 13% higher
simultaneous removal of coke via CO2 gasification ensures mini- conversion values (Reddy et al., 2012).
mization of carbon deposition and generation of undesired COx Another widely investigated series are the vanadium-based cat-
species. alysts. By substituting vanadium in Mg–Al hydrotalcite catalysts,
In another recent patent invention, Arnold et al. (2014) the Mg–V–Al mixed oxides with high surface area and mesoporous
described a process of incorporating oxygen (via an oxygen characteristics were produced, and found to be favorable for the
selective membrane reactor, preferably made from fluorite or ethylbenzene dehydrogenation to styrene under CO2 flow (Carja
perovskite-based mixed oxides) along with CO2 to promote ODE et al., 2003). Moreover, V5+ was identified to be the active site
to styrene. The oxygen sources can be from high- or low-purity O2 , for the dehydrogenation process (Carja et al., 2003). The major
enriched and atmospheric air. In fact, the supplemented oxygen properties of this catalyst are the weak Lewis acid sites con-
can provide partial exothermic heat to the reaction, thus lower- tributed by aluminum, which reduce the catalyst deactivation, in
ing the energy requirement of this reaction, besides maintaining addition to its high surface area contributed by the mesoporous
the high selectivity afforded by CO2 (Arnold et al., 2014). The characteristics.
presence of an oxygen selective membrane reactor can provide Vanadium was also doped on titanium oxide using the acid-
advantages, such as continuous injection of oxygen from various catalyzed sol gel technique, which was shown to be an effective
points along the membrane reactor, thus minimizing the proba- technique to systematically synthesize the catalyst at the required
bility of hot spots in the catalyst bed. This invention was followed ratio (Li et al., 2009). The authors demonstrated that the optimal
by a more comprehensive process configuration, which is inclu- loading of 6 mol% V5+ resulted in diminution of the particle size
sive of a separator section including condenser, compressor, and favoring formation of small crystallites, caused by incorporation
water as shift unit capable of converting the CO contained in the of vanadia into TiO2 .
off-gas stream to more H2 and CO2 in order to recycle back the Capitalizing on the oxygen vacancy effect, Rao et al. (2009)
CO2 into the process. Moreover, a multi-function catalyst capa- and Burri et al. (2013) investigated the effect of ceria on the
ble of simultaneous hydrocarbon dehydrogenation as well as CO structure and catalytic CO2 -ODE reaction activity of V2 O5 /TiO2 –
oxidation (preferably noble metal based) is utilized in this process ZrO2 catalyst. This research group had previously noted that
(Arnold et al., 2014). titania–zirconia mixed oxides exhibited excellent catalytic activity
and selectivity for the CO2 -ODE to styrene reaction in view of the which causes eventual catalyst deactivation and plugging of the
high specific surface area, good acid–base and redox properties, reactor (Zhu et al., 2008):
coupled with the mechanical and thermal stabilities of the TiO2 –
ZrO2 mixed oxides (Burri et al., 2007; Reddy et al., 2008). In their CH4 → Cads + 2H2 ∆H298
◦
= 75 kJ mol−1 (4.4)
catalyst system, the formation of crystalline ZrTiO4 spinel phase
2CO → Cads + CO2 ∆H◦298 = −173 kJ mol −1
(4.5)
along with ZrV2 O7 and CeVO4 phases was also observed. A high
product selectivity of 98% and ethylbenzene conversion of 56%
were obtained over the ceria-doped catalyst. The presence of ceria Transition metal catalysts, such as Ni, are known to be highly
was found to be critical in retarding the catalyst deactivation rate active in the catalytic DRM reaction and comparable to noble
due to its redox properties, which minimized carbon deposition. metal catalysts. However, the transition metal catalysts are suscep-
In addition, Burri et al. (2007) have also explored the use tible to carbon deposition (Wang et al., 2014b). Therefore, great
of high surface area mesoporous silica, such as SBA-15 sup- importance is placed on design and synthesis of highly active, sta-
ports for the redox-based CeO2 –ZrO2 mixed oxide catalysts. ble, and economically viable catalyst system, which can inhibit the
A significant enhancement in ethylbenzene conversion from 21 coke formation while maintaining high catalytic activity for the
to 65% at reaction temperatures ranging from 723 to 923K DRM reaction.
could be observed in their catalyst system. The catalyst redox Van et al. (2006) described a process for the combined reform-
nature ensured greater oxidation–reduction activity at the higher ing of steam with CO2 for hydrocarbon reforming. The process
temperatures based on the surface changes, which evolved and temperature is maintained by routing part of the hot product gas
resulted in greater availability of surface oxygen (Burri et al., from partial oxidation reaction which takes place at the exterior
2007). of the reactor tubes in the reactor vessel. In general most of the
MCM-41, another type of mesoporous silica, has also been processes for steam reformers can be adapted for CO2 reform-
employed as a high surface area support for vanadia catalysts (Qiao ing. In terms of reactor design, the inner passageways are metal
et al., 2009). An improved catalyst dispersion on the mesoporous conduits aligned co-axially with the reactor conduit, and are capa-
silica compared to the conventional silica support was proven by ble of facilitating heat transfer (from partial oxidation reaction)
Raman spectra, which showed the presence of strong bands of to the reformer. In a recent invention, Olah and Prakash (2013)
isolated tetrahedral VO4 (Qiao et al., 2009). advocated the method of forming methanol, in which the DRM
reaction is combined with the conventional steam reforming of
methane at a specified ratio in a process described as bi-reforming
CO2 (dry) REFORMING OF HYDROCARBON/ALCOHOL
reaction. In this reaction, the methane, CO2 , and water are reacted
CO2 REFORMING OF METHANE
in the ratio of 3:2:1 as shown below:
Methane is the simplest hydrocarbon molecule, of which hydro-
gen is the main product. Steam reforming of methane is the most
3CH4 + 2H2 O + CO2 → 4CO + 8H2
common reaction, which is in industrial application. However,
in view of global warming phenomenon due to excessive green-
house gas emission, CO2 dry reforming of methane (DRM) has The bi-reforming reaction catalyzed on a Ni-supported on
emerged as an attractive alternative. DRM reaction results in pro- high surface area or nanostructured support is able to suppress
duction of syngas (consisting of H2 and CO in the ratio of 1:1) coke formation and produces syngas in the ratio of 2H2 :CO
(Eq. 4.1) and can be used as an important feedstock for indus- (Olah and Prakash, 2013). This ratio is the right amount required
trial processes, such as hydrocarbonylation and hydroformulation for methanol production, which is used as a building block in
reactions (Vasant and Kartick, 2006). the chemical industry. Besides, methanol also provides an envi-
Dry reforming of methane is a highly endothermic reaction ronmentally friendly alternative to diesel fuel due to its cleaner
(Eq. 4.1), and thus performs better at higher temperature espe- emission.
cially in the range between 700 and 900°C (Bradford and Vannice, In order to ensure thermoneutrality of the process, air/O2 -rich
1999): gas can be supplied to the system. In fact, Saudi Arabian Oil Co.
has filed for a patent application on the utilization of a multi-
component catalyst system comprising Ni, Rh, Re, and Pt metals
CO2 + CH4 → 2CO + 2H2 ∆H298
◦
= 247 kJ mol−1 (4.1)
with Ce2 O3 , La2 O3 , and ZrO2 mixed oxides to reform petroleum
fuel to H2 -rich syngas. Combustion, steam, and/or CO2 reforming
The main side reaction involved is the simultaneous occurrence
of the petroleum-based fuel is carried out simultaneously in the
of RWGS reactions (Eq. 4.2) that produces more CO. The steam
interior zone of a reactor for syngas production (Al-Muhaish et al.,
produced plays a role in gasifying carbon deposited in the reaction
2015).
(Eq. 4.3):
Noble metals
CO2 + H2 → CO + H2 O ∆H298
◦
= 41kJ mol−1 (4.2)
Dry reforming of methane process generally is catalyzed by either
C + H2 O(g) → CO + H2 ∆H298
◦
= 31 kJ mol−1 (4.3) noble metals (Rh, Ir, Pt, Rh) or some transition metal catalysts,
such as Ru and Ni. Noble metals are used for their resistance to
Methane dissociation (Eq. 4.4) as well as CO disproportiona- corrosion and oxidation, high activity, and good carbon resistance
tion (Eq. 4.5) is the main reactions involved in carbon deposition, (Obradovic et al., 2013).

A series of noble metal catalysts (Rh, Ru, Ir, Pt, and Pd) sup- of Pt/ZrO2 < Pt/TiO2 << Pt/γ-Al2 O3 . Hence, even though Pt is
ported on alumina–magnesia spinel compound was studied by a noble metal, these findings indicate that deposition of car-
Rezaei et al. (2006). Rhodium and ruthenium were shown to bon which blocks the active metal site was the main cause of
exhibit high activity and stability compared to the rest. This was deactivation of the platinum-supported catalysts.
attributed to the formation of more reactive carbon, which was In addition, there have been studies on the low metal loadings
identified as Cγ or superficial carbide. On the other hand, the of the noble metals as means of reducing the implications of cost.
lower stability of Pd catalyst was caused by the formation of less For instance, Bitter et al. (1999) utilized a loading as low as ca. 0.5–
reactive whisker carbon. Zhang et al. (1996) studied the effect of Rh 1 wt% Pt on zirconia to study deactivation and coke accumulation
catalysts and found the specific activities to be strongly dependent during DRM reaction. They found that the size of the Pt particles
on catalyst support as well as the metal particle size (Zhang et al., and the stability of the carbonates formed on the support (from
1996). In general, the activities were found to increasing with metal CO2 activation) to be the critical factors in influencing carbon
particle size. By using different kinds of support, it was found that formation rate. Smaller Pt particles as well as supports favor-
the deactivation rates showed decreasing order of Rh/TiO2 > > ing carbonate formation are favorable in promoting the catalyst
Rh/Al2 O3 > Rh/SiO2 . The poor stability of Rh/TiO2 was attrib- stability during the DRM reaction.
uted to its strong metal support interaction (SMSI) effect, whereas
the inert nature of the SiO2 support resulted in an almost negligible Ni supported metal oxide
metal support interaction. However, in order to enhance the catalytic performance, without
Yokota et al. (2002) were another group who studied the doubt higher loadings of active metals are required. Nickel, among
effect of Rh catalyst and found that higher surface area sup- non-noble metals, is the only one from Group 8 transition metals
ports were vital to improve Rh dispersion. With increasing Rh that has comparable activity to noble metals (Gao et al., 2011).
dispersion, turn over frequency (TOF) was found to decrease. Nevertheless, as aforementioned, nickel catalysts are more suscep-
Therefore, TOF for CH4 conversion decreased in the order tible to catalyst deactivation due to carbon formation. As such, an
of Rh/TiO2 > Rh/La2 O3 = Rh/CeO2 > Rh/ZrO2 = Rh/MgO = immense requirement for investigation on suitable catalyst sup-
Rh/SiO2 = Rh/MCM-41 > Rh/γ-Al2 O3 . Detailed investigations ports or promoters to be used to eliminate the extensive carbon
using XANES revealed that Rh existed as metal on TiO2 whereas Rh formation on Ni-based catalysts.
on Al2 O3 possessed a cationic character. This led to a conclusion Several studies have been carried out in order to rationally
that Rh was structure sensitive in DRM reaction. synthesize Ni-based catalysts in order to provide high activity
Mark and Maier (1996) found that TOF over Rh, Ru, Ir, Pt, or and improved carbon resistance. Some of the nickel-based cata-
Pd-supported catalysts did not significantly depend on metal dis- lysts synthesized include bimetallic catalyst, supported Ni catalyst,
persion, which is in contrast with the results of Yokota et al. (2002). perovskite-based and Ni core–shell structured catalysts.
They observed that the support was only influencing the stabiliza- According to Ruckenstein and Hu (1996), addition of various
tion of metal surface area, which was responsible for the catalyst promoters, such as La2 O3 , MgO, BaO, and CaO to the catalyst
activity. Hence, they postulated that under reaction controlled system are found to benefit DRM activity in terms of decreasing
temperatures, it was sufficient to consider only the accessible metal coke formation (Pakhare et al., 2014). Similarly, Zhao and Wagner
surface area. (2004) have patented the calcium promoted Ni supported on cal-
Erdöhelyi et al. (1994) conducted an in-depth investigation on cium aluminate catalyst for the CO2 -steam reforming of methane.
Pd-based catalyst for CO2 reforming of methane. According to The Ni supported on calcium aluminate catalyst was found to
them, the decomposition of methane resulted in yielding hydro- be not only coke resistant, but also able to tolerate sulfur com-
gen and small amounts of ethane and ethlyene. Although carbon pounds at concentrations between 1 and 20 ppm. The calcium
deposition was observed, however, at the stoichiometric feed ratio promoter was able to enhance the catalyst surface and porosity
(1/1) of CH4 and CO2 , the amount was rather low. Therefore, and displayed higher activity index compared to conventional Ni
they concluded that at high reaction temperatures, Pd supported supported on alumina catalysts. Moreover, addition of these pro-
catalysts exhibit high catalytic activity with no or only very little moters can result in strong metal–support interaction, as well as
carbon deposition. lattice oxygen mobility, which are of prime importance in this
Platinum (Pt) supported catalyst was also widely investigated reaction. For example, promotion of Ga2 O3 on inert SiO2 sup-
for the DRM reaction. Souza et al. (2001, 2002) investigated on port resulted in activation of CO2 , thus forming surface carbonate
Pt/Al2 O3 and Pt/ZrO2 catalysts for DRM reaction. They found that and hydrogen carbonate species which provided higher catalytic
Pt/Al2 O3 catalyst showed fast deactivation during DRM reaction stability and coke resistance on Ga2 O3 -promoted SiO2 -supported
as a result of high carbon deposition rate. However, by intro- Ni catalyst (Pan et al., 2010). In another study, Mo et al. (2014)
ducing a small amount of ZrO2 (>5%) to Pt/Al2 O3 catalyst, studied the effect of La2 O3 on SiO2 supported Ni nano-catalyst.
the activity and stability were tremendously improved. The pres- The Ni nano-catalyst was synthesized using a facile and econom-
ence of Pt–Zrn+ interfacial sites was the main reason attributed ical in situ self-assembled core–shell precursor route via incipient
to low carbon deposition, which rendered higher stability and wetness co-impregnation method. In this method, oleic acid was
activity of ZrO2 promoted Pt/Al2 O3 catalyst. In fact, Bitter et al. used to ensure formation of Ni nanocatalysts with particle sizes
(1999) and Nagaoka et al. (2001) also reported that the stability of less than 3 nm. The catalytic DRM performance could be signif-
Pt catalysts increased in the order of Pt/ZrO2 > Pt/TiO2 > Pt/γ- icantly improved with promotion of only 1 wt% La2 O3 , whereby
Al2 O3 , whereas the carbon formation rate decreased in the order near equilibrium CO2 and CH4 conversions (above 80%) at 973 K
could be achieved. Furthermore, due to the good catalyst disper- can be prepared by various techniques including co-precipitation,
sion, negligible carbon deposition could be attained even after sol gel, impregnation, and homogeneous precipitation.
100 h on stream at gas hourly space velocity of 72,000 g. Similarly,
the positive influence of the basic borated–alumina (B2 O3 –Al2 O3 ) Perovskite catalysts
supported Ni-catalyst profoundly influenced the catalytic DRM Another group of structured type catalysts, i.e., perovskite-type
performance (Ni et al., 2012). The authors proposed that the sur- represented by the general formula ABO3 have been widely inves-
face hydroxyl (OH) groups present on the catalyst surface were tigated for high-temperature reactions, such as DRM due to their
crucial in oxidizing surface carbon species from dissociation of high thermal stability (Pena and Fierro, 2001, Moradi et al., 2014).
methane molecules in order to maintain catalytic stability. In general, the B-site cation is surrounded octahedrally and the
The importance of basicity was explored by another recent A-site cation is located in the cavity made between these octahe-
investigation on the effect of Sr over the catalytic DRM perfor- dral sites. The lattice parameter and unit cell dimensions can be
mance of Ni–La2 O3 catalysts (Sutthiumporn and Kawi, 2011). modified by A-site ion substitution in these structures offering the
The Sr-doped Ni–La2 O3 catalyst significantly enhanced the DRM possibility of varying the dimensions of the unit cell. Thus, accord-
process even temperatures as low as 873 K coupled with low car- ingly, the covalence of the B–O bond in the ABO3 structure can
bon deposition. The highly mobile surface oxygen species present be modified (Fan et al., 2009). Replacement of A- and/or B-site
on the catalyst system played an important role in C–H activa- cations by other metal cations leads to formation of lattice defects,
tion for the higher activity, and adsorbing adsorb CO2 molecules which are crucial for O2 -adsorption and oxygen mobility within
in order to form bidentate carbonate species for carbon removal the crystal structure, in order to promote catalytic activity.
(Sutthiumporn and Kawi, 2011). Similarly, alkaline promoter, such For the DRM reaction, the perovskite catalyst structure gener-
as magnesium oxide, was also studied on the Ni/La2 O3 systems. ally consists of rare earth elements, such as lanthanum in the A-site,
In fact, it is widely known that MgO possess basicity and has the and transition metal elements, such as nickel (active centers for
same crystal structure as NiO, hence can easily form the non- methane activation) in the B-site. According to Batiot-Dupeyrat
reducible basic solid solution of Nix Mg(1-x) O, which is important et al. (2003), the LaNiO3 perovskite-type oxide is reduced under
to improve basicity and catalyst dispersion (Arena et al., 1991). hydrogen atmosphere in three steps. In the first reduction step
Based on the study by Ni et al. (2013), the loading of 5 wt% Ni (200–500°C), La4 Ni3 O10 phase is formed, while the second step
on a MgO promoted La2 O3 support at the optimal mole ratio (600–650°C) leads to the formation of the spinel-type La2 NiO4
of 10 Mg2+ /La3+ resulted in generation of highest amount of phase. The final step (680–750°C) coincides with decomposi-
monoclinic lanthanum oxycarbonate species and surface adsorbed tion into La2 O3 and Ni metal. The consecutive reaction steps are
oxygen ions which are able to oxidize deposited carbon (Ni et al., summarized as shown below:
2013).
Ni◦ + La2 O3 + CO2 ↔ CO + La2 NiO4 (4.6)
Bimetallic catalysts CH4 + La2 NiO4 → CO + 2H2 + La2 O3 + Ni◦ (4.7)
Bimetallic structures involves alloying with a second metal (either
a noble metal or another transition metal) in order to modulate The well-defined perovskite structure and their interesting
the catalyst properties by causing a “synergistic” effect between redox properties and accessibility enable attainment of nanometer
the two metals (Sankar et al., 2012). For instance, the effect of sized metallic particles under reducing environment (Valderrama
Pd on Ni-based catalysts supported on yttria was tested by Oemar et al., 2010). Thus, this leads to desirable properties to maintain
et al. (2011) for the oxidative DRM reaction. The bimetallic Pd–Ni catalytic activity and stability under the high-temperature reaction
species enhanced the metal support interaction. Furthermore, the environment. The La2 NiO4 perovskite-type catalyst (with A2 BO4
presence of α-oxygen on Y2 O3 surface played an important role structure) was found to demonstrate higher catalytic activity com-
in C–H bond scission of CH4 as well as oxidation of the deposited pared to supported Ni/La2 O3 or LaNiO3 catalyst due to formation
carbon. However, the surface α-oxygen amount is very low; hence a of even smaller nickel particle after reduction (Gallego et al., 2006).
small amount of oxygen was co-fed for the DRM reaction in order The reduction treatment is an important parameter to mitigate
to ensure regeneration of the α-oxygen and thus maintaining the carbon deposition on the La2 NiO4 catalyst. This is due to limi-
stability of the catalyst. tation in La2 O3 sites for the un-reduced La2 NiO4 catalyst, which
Besides noble metals, other transition metals can also be used resulted in lower CO2 activation in order to completely facilitate
to form alloyed bimetallic structures. For example, Zhang et al. carbon removal.
(2007b, 2008) synthesized various Ni–Me (Me = Co, Fe, Cu, or In fact, both the A-site and B-site of the perovskite catalyst
Mn) bimetallic catalysts in the hydrotalcite structure of Ni–Co– can be substituted in order to enhance the catalyst performance.
Al–Mg–O using the coprecipitation method. Ni–Co was shown Sutthiumporn et al. (2012) found that lattice oxygen species in
to exhibit the best results with respect to DRM catalytic stability the partially substituted Lax Sr1-x Niy Me1-y O3 (Me = Fe, Cu, Co,
and activity. A 2000-h DRM catalytic stability test was successfully Bi) perovskite catalysts are crucial in activating the C–H bond
conducted with negligible catalyst deactivation. This bimetallic of the CH4 molecule for improved reactant conversion at lower
catalyst composition containing the dual-active catalyst compo- temperature DRM reaction. In addition, carbon formation can be
nents of Ni and Co and tested active for DRM was patented by the suppressed due to the reaction with CO2 to form La2 O2 CO3 . Sub-
authors and tested for high gas hourly space velocity between 2000 stitution of Cu to the LaSrNiO3 catalyst was found to initially
and 2,000,000 ml/gcat h-1 (Wang et al., 2011). This catalyst system display high CH4 conversion; however, particle agglomeration

resulted in subsequent carbon formation causing lower catalytic high-temperature reactions due to enhanced resistance to sintering
stability. On the contrary, substitution of Fe resulted in high activ- caused by partial blocking by the peripheral silica shells. However,
ity and stability at prolonged reaction time (despite low initial just recently, attempts have been made for investigating such cat-
activity) owing to increased mobility of lattice oxygen species alysts for DRM reaction. Li et al. (2014a) developed Ni-at-SiO2
under the reducing reaction environment. core–shell catalysts and investigated effect of shell thickness modi-
Spinel-type oxide Ni-based catalysts of formula ABO4 or fications for the DRM reaction. Formation of nickel phyllosilicate
A2 BO4 are variations to the structured cubic perovskite (Corthals species was found to impart high catalytic stability at 1073 K due to
et al., 2008). The sub-stoichiometric spinel structures possess high strong interaction between Ni core and silica shell (Li et al., 2014a).
activity due to high dispersion of NiO into the spinel and thermal In a further progress, Li et al., 2014b) successfully tuned the specific
stability. Gallego et al. (2008) exhibited high catalytic activity using surface area in order to achieve specific surface area controllable
reduced La2 NiO4 as catalyst precursor for DRM at 973 K, with a Ni-at-Ni embedded SiO2 , yolk shell nanocomposites, which lead
conversion rate of 85 and 93% for CH4 and CO2 , respectively, and to higher specific surface area, higher Ni dispersion, and stronger
inhibition of carbon formation even after 160 h of experiment. interaction between Ni species and SiO2 . The preparation method
Based on their explanation, the absence of carbon deposition was involved a facile self-templating method via the transformation
due to the enhanced reaction between La2 O2 CO3 and the Ni–CHx of Ni phyllosilicate, which displays greater DRM reactivity due to
species, thus producing the product syngas. Moreover, formation easier access of reactants to Ni active sites. These desirable proper-
of the small nickel particles (average diameter of 7 nm) upon ties led to improved conversion and high stability even at the lower
reduction was crucial in preventing agglomeration and site for reaction temperature of 973 K (Li et al., 2014b). Since basicity is an
carbon growth. important factor especially for CO2 activation and further carbon
Spinel structures such as NiAl2 O4 formed as a result of high- gasification, Li et al. (2014c) further treated Ni@SiO2 nanopar-
temperature calcinations result in SMSI (Jimenez-Gonzalez et al., ticles with Mg(NO3 )2 forming Ni–Mg phyllosilicate shell. The
2015). However, they require high reduction temperature for cat- treatment duration of 10 h was found to be the optimal treatment
alyst activation. Moreover, according to Bhattacharyya and Chang time in order to ensure sufficient exposure of active Ni metal,
(1994), the γ-alumina in the NiAl2 O4 spinel structure formed while at the same time, stabilizing the Ni particles. This method
via solid-state reaction can lead to gradual transformation to was successfully applied for DRM reaction at 973 K, achieving high
the α-phase especially over prolonged reaction time at high- catalytic activity and stability, with negligible carbon deposition
temperatures. This causes a decline in catalyst performance due even after 95 h time on stream.
to sintering of the alumina support. In order to overcome this
phenomenon, LaAlO3 perovskite oxide phase was pre-formed on
CO2 (dry) REFORMING OF ETHANOL
alumina-based support and upon calcinations and further impreg-
Besides methane, CO2 reforming of alcohols, especially ethanol
nation with Ni, a predominantly “inverse” surface nickel aluminate
have begun to attract considerable research interest in recent years.
was formed. The formation of this phase could favorably hinder
Ethanol has been proposed as raw material for various applications
the phase transformation of the γ-alumina to undesirable lower
in recent years, since it can be feasibly produced from various bio-
surface area α-alumina phase (Kathiraser et al., 2013a,b).
mass sources, such as energy crops, residual materials from agro-
Pakhare et al. (2013a) have recently reported the synthesis of
industry or forestry, and organic/gasifiable fractions of municipal
structurally stable lanthanum-zirconate pyrochlores (La2 Zr2 O7 ).
solid waste via biochemical processes (Jankhah et al., 2008). Most
In general, the pyrochlore structures (A2 B2 O7 ) are crystalline ther-
of the catalytic studies in recent years focus on steam reforming
mally stable ternary metal oxides with a cubic unit cell. Typically,
of ethanol. However, the growing interest in CO2 reforming of
the A-site is a rare-earth element (such as lanthanum) and the
ethanol augurs well in terms of socio-environmental considera-
B-site consists of a transition metal element with smaller ionic
tions to reduce greenhouse gases and make this a truly sustainable
radius. CO2 activation on La site of the Rh modified lanthanum-
process.
zirconate pyrochlore was proven (by means of isotopic pulsing)
There are several advantages associated with CO2 reforming of
to take place via formation of three polymorphs (types I, Ia, and
ethanol, such as being renewable, biodegradable and easily trans-
II) of La2 O2 CO3 , of which only type II is reactive. The authors
portable, and compared to methane (which is non-renewable and
have also studied the interesting effects on DRM reaction by pro-
highly explosive), ethanol is comparatively less dangerous and
motion with metals, such as Rh, Pt, and Ru in the pyrochlore
toxic (Wu and Kawi, 2009). Hence, ethanol can be considered as an
structure (Gaur et al., 2012; Pakhare et al., 2013b). These effects
economically viable alternative green power source, which results
include (i) formation of vacancies at the O sites during synthesis,
in low pollutant emissions and controlled combustion (Tsiakarasa
which enhance oxygen ion migration, thus minimizing oxidation
and Demin, 2001). In addition, relatively lower temperatures are
of deposited carbon and (ii) the ability to isomorphically sub-
required for a thermodynamically favorable reaction, where DRE
stitute the catalytically active Rh, Pt, and Ru metals into B-site,
is thermodynamically favorable above 318°C, compared to DRM
whereby they do not sinter at high DRM temperatures (Pakhare
(above 642°C) (Puolakka and Krause, 2007).
et al., 2014).
The main reactions involved in DRE are as follows:
Core–shell catalysts
Core–shell type of catalysts in the form of metal-at-metal C2 H5 OH + CO2 → 3CO + 3H2 ∆H298
◦
= +339.60 kJ mol−1
oxide nanoreactor structure has been widely studied for (4.8)
In this stoichiometric reaction, syngas is produced in a theo- reaction temperature, gas hourly space velocity, and catalyst parti-
retical ratio of 1:1, which is similar to DRM process, thus mak- cle size is crucial in affecting the condition of the deposited carbon
ing it suitable for production of some liquid hydrocarbons or (Rostrup-Nielsen et al., 2002; de Llobet et al., 2015). In fact, based
oxygenated hydrocarbons (Zhu et al., 2008). on a cost analysis conducted by Abatzoglou et al. (2006), it was esti-
However, other types of side reactions are also prone to take mated that the break even cost for a techno-economically sustain-
place in parallel during the DRE reaction, such as ethanol decom- able process of multi-walled carbon nanotube production from
position, dehydration reaction, and RWGS reaction (Wu and Kawi, ethanol dry reforming can reach a price of around US$1.0/kg car-
2009): bon nanotube. From the reaction (4.16) quoted, carbon formation
is targeted along with syngas.
C2 H5 OH → CH4 + CO + H2 ∆H298
◦
= +49 kJ mol−1 In these reforming conditions, the syngas ratio is lower than the
(4.9) complete dry reforming process (Eq. 4.1), but it sequesters the CO2
C2 H5 OH → C2 H4 + H2 O ∆H298
◦
= +45 kJ mol−1 carbon in an inert solid form, which is readily removable from the
(4.10) non-porous catalyst surface (Abatzoglou et al., 2006). Therefore,
if the quality of the carbon sequestered is high enough in the form
CO2 + H2 → CO + H2 O ∆H298
◦
= −39.5 kJ mol−1 of carbon nanotubes, then it would constitute a major revenue
(4.11) source besides synthesis gas as energy vector or raw material for
chemicals synthesis and also the associated carbon sequestration
Generally, the goal of this reaction is to maximize hydrogen
credits (Abatzoglou et al., 2006).
production. Based on the reaction enthalpies, we can see that
However, when syngas production is the desired outcome, it
reaction 4.8 is the most kinetically favored at high-temperatures
should be noted that higher hydrocarbons generate more car-
compared to reactions 4.9 and 4.10 (favored at intermediate reac-
bonaceous species. For example, via steam reforming reactions,
tion temperatures) and reaction 4.11 (favored at low-reaction
thermodynamic calculations reveal that 1.17 mol C/mol butanol
temperature).
could be observed at 573 K (for steam reforming of butanol at
Carbon deposition is also prevalent issue in the DRE reaction
water-to-butanol ratio of 1) compared to 0.58 mol C/mol ethanol
and the reactions pertaining to carbon deposition are ethanol
at the same conditions for steam reforming of ethanol (Wang,
decomposition (Eq. 4.12), methane decomposition (Eq. 4.13),
2011). Operational parameters can further influence the outcome
ethylene polymerization (Eq. 4.14), and Boudouard reaction
of the reaction. For example, the effect of temperature on car-
(Eq. 4.15):
bon formation was analyzed thermodynamically by Jankhah et al.
C2 H5 OH → C + CO + 3H2 ∆H298
◦
= +125 kJ mol−1 (2008), and thermodynamically, a drastic drop in carbon yield
(4.12) takes place above 550°C, especially at greater CO2 /ethanol ratio at
temperatures above 750°C.
CH4 → 2H2 + C ∆H298
◦
= +75 kJ mol−1
(4.13) Catalyst selection for DRE
C2 H4 → Polymerization → Coke (4.14) Similar to DRM reaction, noble metals and Ni-based catalysts play
an important role in the catalytic conversion of DRE reaction,
2CO → CO2 + C ∆H298
◦
= −171 kJ mol −1
whereby optimization studies of these catalysts are important in
(4.15)
order to achieve high activity and selectivity, as well as overcome
As we can see, the above carbon producing reactions are mainly catalyst deactivation.
from by-products of the initial reactions. In fact, the carbon can be In terms of noble metal catalysts, Rh has been shown to dis-
harnessed as carbon nanotube, a material which is rapidly gain- play high activity, stability, and low coke formation for the CO2
ing widespread attention due to its many features, such as high reforming of methane and steam reforming of ethanol reactions.
porosity, high mechanical strength, high thermal conductivity, In fact, in terms of steam reforming of ethanol, the order of activity
low-specific weight, and chemical inertness, and is promising for for metals is as follows: Rh > Pd > Ni ~ Pt (Wu and Kawi, 2009) As
potential applications in chemistry and physics (Blanchard et al., such, Wu and Kawi (2009) studied the DRE reaction with ultra-low
2008; Khavarian et al., 2014). Blanchard et al. (2008) described a loading of 1 wt% Rh supported on Ce incorporated SBA 15 cata-
process whereby CO2 was reformed with ethanol to syngas and lysts. As aforementioned, the main benefits of mesoporous silica
a part of the CO2 was “sequestered” under the form of carbon supports such as SBA 15 are their high surface area, uniform pore
nanofibers (CNF) and multi-walled nanotubes (MWNT).Their size which is tunable from 4.6 to 30 nm and thick wall (around
reaction mechanism was targeted to be as follows: 4 nm) (Wu and Kawi, 2009); which place emphasize on their
enhanced stability rendering properties. Furthermore, by incor-
3C2 H5 OH + CO2 ↔ 5CO + 9H2 + 2C (4.16) porating Ce in the SBA 15 structure, the surface oxygen mobility
of the catalyst surface can be enhanced due to the redox ability
The formation of carbon during catalytic reforming can be of of the Ce4+ ↔ Ce3+ species (Lee et al., 2008). The key factors
various types, i.e., graphitic, amorphous, resinous, coal-like, fila- behind the successful implementation of Rh/Ce-SBA 15 catalysts
mental, and nanotubes. Hence, it is crucial that in order to obtain for syngas production from dry reforming of ethanol (DRE) are
optimally pure and homogeneous of the end product, precon- due to the mobility of surface oxygen species (attributed to Ce
ditioning, and optimal setting of reforming parameters, such as incorporation in SBA 15) as well as the good dispersion of Rh over

the Ce/SBA 15 catalyst support. The highest amount of hydrogen carbon compared to the rest of the catalysts, proven based on
production was achieved at the optimal Ce/Si molar ratio of 1/20. Raman and SEM analysis. The fine dispersion of Nio on this sam-
Even upon increasing the reaction temperature up to 750°C, the ple characterized by the smaller Nio particles suggest the favoring
hexagonal mesopores of the Ce/SBA 15 structure was found to toward formation of filamentous carbon at low growth rate, due
remain intact. to the low driving force for carbon diffusion through small crystals
In another study, CO2 as a co-feed to ethanol steam reforming (Zawadzki et al., 2014).
was carried out over Pt/ceria catalysts (de Lima et al., 2010). Com- Carbon steel catalysts have also been explored for the DRE
pared to Ni-based catalysts, carbon diffusion does not take place reaction for hydrogen and carbon nanotube production. Oliveira-
on noble metals, however, carbon may encapsulate the metal parti- Vigier et al. (2005) investigated the use of recyclable and long-
cle or cover the support, thus causing catalyst deactivation. In view lasting SS 316 catalyst for DRE reaction and successfully obtained
of this, de Lima et al. (2010) studied the effect of adding CO2 to a hydrogen yield that is 98% of the theoretical value. Likewise,
the feed in order to shift the equilibrium in favor of the reactants, Blanchard et al. (2008) and Jankhah et al. (2008) have also used
which can help mitigate carbon deposition. Via this approach, they carbon steel catalyst to evaluate the production of syngas and
proposed that CO2 may be recirculated from the outlet stream nanocarbons via DRE. High yields of hydrogen and carbon could
of the proton exchange membrane fuel cell. The positive effects be produced at the relatively low temperature of 550°C. In sum-
of CO2 in favoring catalytic stability and favoring formation of mary, ethanol decomposition and dry reforming were the main
CO and acetaldehyde over carbon deposits were clearly demon- reaction pathways for the production of hydrogen and carbon
strated based on the IR bands obtained over DRIFTS spectra. In nanotube via carbon steel catalyst for the DRE reaction. Based
brief, the ethoxy species undergo ODH to acetate via addition on the TEM results of carbon nanofilaments (CNFs) obtained
of O provided by the support from species such as by bridging from ethanol dry reforming, Jankhah et al. (2008) concluded the
OH group (during steam reforming) or O adatom by CO2 dis- following:
sociation at vacancies (during dry reforming). Hence, the acetate
further undergo demethanation to form carbon intermediates and (1) The CNFs consist of graphite sheets that not concentric to the
further reform CHx species. Hence, a carbon cleaning mechanism internal empty tube, but instead are rather oblique to the tube
is proposed by the authors, whereby CO2 competes with ethanol axis.
for the same adsorption sites, thus reducing the rate of decomposi- (2) The CNFs are both in the form of rectilinear and helicoidally
tion of the adsorbed intermediate species. Hence, this was found to arranged, and in certain cases, each CNF contain more than
directly impact rate of CHx species formation, thus reducing cat- one grain.
alyst deactivation, by enhancing more CO production (de Lima
et al., 2010). CO2 (dry) REFORMING OF GLYCEROL
Hu and Lu (2009) have studied the DRE reaction over con- Natural gas obtained from shale gas technology is a non-renewable
ventional Ni/Al2 O3 catalysts. Based on their observations, at source of energy which requires energy intensive processing.
CO2 /ethanol ratio of 1, ethanol decomposition dominates, lead- Depletion in fossil fuels and natural gas reserves prompted
ing to CO/H2 ratio much lower than 1. In order to enhance researchers to find ways in utilizing renewable resources for
reforming of ethanol, increasing CO2 /H2 ratio to 5, resulted in reforming processes. In this aspect, biofuels like ethanol and
lowered production of side products such as CH4 , acetaldehyde biodiesel are gaining considerable significance (Wang et al., 2009).
and coke, and facilitated DRM and coke gasification. They pos- Glycerol, an oxygenated hydrocarbon, is a byproduct of the
tulated that employing excess CO2 at high-temperatures could biodiesel production process by transesterification of vegetable
enhance the efficiency of coke elimination and resulted in selec- oils and methanol (Wang et al., 2009). In recent years the process
tivity toward more syngas production. These observations were of producing hydrogen/syngas from glycerol reforming is becom-
consistent with Bellido et al. (2009) who investigated the per- ing increasingly important due to the green chemical properties of
formance of Ni/Y2 O3 –ZrO2 supported catalysts for DRE at var- glycerol such as non-toxic, non-volatile and non-flammable (Kale
ious temperatures and reported that greater selectivity toward and Kulkarni, 2010). Most investigations are based on autother-
syngas production could be achieved by manipulations of the mal/steam reforming of glycerol (Zhang et al., 2007a; Adhikari
system parameters and reaction conditions. This was because car- et al., 2008; Valliyappan et al., 2008), however, in recent years, there
bon accumulation blocks the metallic active sites and enhances is increasing research being carried out for dry reforming of glyc-
ethanol dehydration and thermal decomposition of ethanol, which erol (DRG). This is because steam reforming of glycerol results in
increases the methane and C2 H4 production. significant H2 production with high H2 /CO ratio, thus rendering
Recently, Zawadzki et al. (2014) studied DRE reaction over Ni the reaction products inappropriate for the downstream Fischer
supported on Al2 O3 , CeO2 , MgO, and ZrO2 by impregnating the Tropsch synthesis for production of gasoline. As such, water/steam
oxide with a solution of Ni(NO3 )2 in methanol. Their study was needs to be replaced with CO2 in order to maintain the H2 /CO
aimed to verify the use of methanol in the preparation method and ratio <2 (Siew et al., 2014).
its effect on the different oxide-based supports. Ni/Ce was found Furthermore, research on CO2 DRE has shown that CO2 can
to result in higher syngas production compared to Ni/Al, Ni Zr, be sequestered and carbon deposits in the form of CNFs can be
and NiMg catalysts. However, NiCe also showed the highest pro- formed. These CNFs have commercial potential. Likewise glycerol
portion of filamentous carbon species compared to amorphous dry reforming can also be expected to facilitate CNFs production
(Kale and Kulkarni, 2010). These high values inert carbon can This catalyst composition was also found to display good stability
result in removal of CO2 from the carbon biosphere cycle (Wang over a 72-h test run at 1023 K at a weight hourly space veloc-
et al., 2009). ity of 3.6 × 10-4 ml g-1 h-1 STP (Siew et al., 2015). Kinetic studies
According to Wang et al. (2009), the main reactions which may showed that glycerol decomposition and glycerol dehydrogena-
take place during DRG are as follows: tion as the most probably competing route in a parallel pathway
◦
for syngas production. Methane was also produced as a byproduct
C3 H8 O3 ↔ 4H2 + 3CO ∆H298 = +251.18 kJ mol−1 from glycerol dehydrogenation. The authors proposed that CO2
(4.17) played a role in promoting RWGS reaction (Siew et al., 2014).
CO + 3H2 ↔ CH4 + H2 O
◦
∆ H298 = −206.11 kJ mol−1 In another recent study, Lee et al. (2014) investigated the use of
(4.18) cement clinker-supported Ni catalyst with various loadings for
◦ DRG reaction. Physicochemical analysis techniques revealed that
CO2 + 4H2 ↔ CH4 + 2H2 O ∆H298 = −164.94 kJ mol−1 cement clinker was a complex mixture of CaO (62%) and SiO
(4.19) (17%) oxide compounds. They found that Ni loadings of 20 wt%
◦
CO2 + CH4 ↔ 2H2 + 2CO ∆H298 = +247.28 kJ mol−1 led to desirable syngas production with H2 /CO ratio of 1.5 and
(4.20) low methane selectivity at 1023 K (Lee et al., 2014).
◦
CO + H2 O ↔ H2 + CO2 ∆H298 = −41.17 kJ mol−1 FUTURE PERSPECTIVES
(4.21) In terms of catalyst development, there still exists room for
◦
C + H2 O ↔ H2 + CO ∆H298 = +131.26 kJ mol−1 improvement in terms of catalyst development with superior
(4.22) catalytic activity, selectivity and stability (minimum carbon depo-
◦ sition), albeit at a low cost. This can be achieved via synthesis of
CH4 ↔ 2H2 + C ∆H298 = +74.85 kJ mol−1
embedded core–shell type catalysts. The encapsulation of active
(4.23)
◦
metal nanoparticles in the cavities of porous structures provides an
CO + H2 O ↔ H2 + CO2 ∆H298 = −41.17 kJ mol−1 alternative feasible route for the design of core–shell type catalysts
(4.24) owing to their large surface area making them ideal for catalysis,
C + H2 O ↔ H2 + CO
◦
∆H298 = +131.26 kJ mol−1 as well as energy storage and conversion applications (Zhang et al.,
(4.25) 2013). As an example, Mo et al. (2014) developed the in situ self-
◦ assembled core–shell precursor route for synthesis of embedded
2CO ↔ CO2 + C ∆H298 = −172.43 kJ mol−1 core–shell catalysts having good dispersion, which is the essential
(4.26) factor in enhancing the catalytic activity and stability, by impart-
◦
C + 2H2 O ↔ 2H2 + CO2 ∆H298 = +74.85 kJ mol−1 ing anti-coking properties for the DRM reaction. This is a good
(4.27) progress in terms of industrial catalyst development. As such, fun-
damental studies, which can provide a clear insight in terms of
Based on the main reactions, we can see that the carbon pro- molecular level understanding of the catalyst geometry and active
ducing reactions are mainly from methane decomposition (Eq. sites, are one of the important aspects that need to be addressed.
4.23) and Boudouard reactions (Eq. 4.26). Thermodynamic analy- Indirectly, insights gained from the fundamental studies are corre-
sis conducted by Wang et al. (2009) and Cheng et al. (2012) showed lated to the implications of cost involved in developing the catalyst,
that temperatures between 800 and 1000 K at 1 atm pressure repre- which is an important factor for process feasibility. The next factor,
sent the best conditions for optimal DRG performance. Methane, which requires much research, is on large-scale production of cat-
an undesirable by product is produced via CO (Eq. 4.18) and CO2 alysts, especially nano-catalysts. Even though the catalyst synthesis
hydrogenation (Eq. 4.19). CO/CO2 hydrogenation being exother- may have been proven in lab scale, however, they require extensive
mic can result in suppression of methane formation at higher fine-tuning for reproducibility and industrial scalability as well
temperatures, and this has been supported by thermodynamic as the need for consideration of environmental factors involved
analysis (Wang et al., 2009). during catalyst synthesis.
Another important limitation that needs to be addressed is
Catalyst selection for DRG in terms of the process energy requirements. The setting up of
Similar to methane reforming reactions, Ni-based catalysts are industrial processes utilizing CO2 for reactions such as ODH and
preferred for glycerol reforming, albeit their propensity for car- reforming is one of the long-term major goals of chemists and
bon deposition. Early studies on steam reforming of glycerol focus engineers alike, in view of the potential long-term global envi-
on Ni supported on various oxide supports such as Al2 O3 , MgO, ronmental benefits. In fact, the current gaps of knowledge stem
MgAl2 O4 , SiO2 , ZrO2 , and CeO2 (Ebshish et al., 2012). In fact, Ni- from the reaction process energy and economic aspects. Hence,
based catalysts can easily cleave the bonds between O–H, –CH2 –, the possible solution for improving the energy aspect is via process
C–C and –CH3 –, thereby possessing high activity for hydrogena- intensification.
tion and dehydrogenation (Lee et al., 2014). Siew et al. (2014) In fact, for steam reforming of methane, Sulzer has developed a
investigated the performance of Ni/Al2 O3 catalysts doped with combined static-mixer reactor consisting of heat transfer tubes
La for DRG reaction at 873 K. They found that only 3% La pro- as well as monolithic catalytic reactors placed within the pip-
motion was sufficient to reduce the carbon deposition by 20%. ing (Stankiewicz and Moulijn, 2000). In another development,

micro-channel catalyst coated reactors have been developed by for separation of oxygen from air which is to be supplied to the
Velocys, also for steam reforming of methane. It was found that chemical process. Catalytic membrane reactors are the strategic
by employing such micro-channel reactors, considerable improve- means for process intensification and thus markedly improv-
ment in terms of contact time of reactor fluid with catalyst which ing the existing replace conventional packed bed reactor based
results in 300-fold increase in production capacity/volume can processes (Fontananova and Drioli, 2010) for CO2 -mediated
be achieved (Tonkovich et al., 2007). These developments for the oxidative high-temperature reactions.
steam reforming of methane reactors are especially beneficial and In terms of process, in order to enhance the conversion of CO2 -
applicable to dry reforming of hydrocarbons/alcohol, as the nature mediated ODH reactions, controlling the contact mode of oxygen
of both steam/CO2 -mediated reactions are endothermic. In this to the reactants is important to improve selectivity toward olefin
approach, noble metal catalysts are directly coated on the metal production (Wang et al., 2006). On the other hand, the combina-
extended surfaces. This integration of heat transfer as well as cat- tion of DRM with partial oxidation is beneficial in tailoring the
alytic dehydrogenation/reforming reaction can lead to supply of syngas product ratio of H2 :CO to 1–2 for further downstream
thermal energy to the catalysts at a rate adequate in maintaining Fischer–Tropsch reactions.
high catalytic activity. Moreover, compared to traditional reform- In order to supply the required oxygen across the membrane,
ers, which require radiation of heat to tubes, followed by heat dense mixed ionic and electronic conducting perovskite-type
conduction through contact resistances to the catalysts (in pellet membranes have much potential since external circuitry is not
form) inside the tubes; the heat transfer ability in catalyzed heat required (Caro et al., 2007). The ceramic oxygen permeable mem-
exchangers can be tremendously improved (Valensa, 2009). branes are highly selective to O2 and catalyze the dissociation of
In terms of process design improvements especially for indus- O2 molecule into oxygen ions, O2- which permeate across the
trial generation of hydrogen, an emerging technology that has membrane based on the O2 partial pressure gradient (Smart et al.,
tremendous advantages to offer is the precious metal monolith 2014). The membrane functions as a distributor of the oxygen,
catalyst for advancement of new steam reformer designs (Farrauto which in its ionic state promotes selectivity toward product for-
et al., 2007). The monoliths with “washcoats,” which contain pre- mation. In other words, lattice oxygen supply from the mixed
cious metals (where the precious metals are well dispersed on high ionic and electronic conducting membranes inhibits combustion
surface area carriers such as thermally stabilized alumina) have and the distributed mode of oxygen supply along the membrane
excellent mechanical and chemical resistance, low pressure drop, channel further prevents formation of hot spots (Yang et al., 2013).
and a more compact size compared to reactors with traditional For example, for CO2 -oxidative coupling of methane reac-
pellets or particulate materials. The need for temperature con- tions, a perovskite membrane which provides O2- supply from
trol can be met by technological advancements in the form of air can selectively convert methane to C2 products, thus avoid-
catalyzed heat exchangers in the reformers. In fact, deposition of ing gas phase reactions and deep combustion of methyl radicals.
highly active noble metal catalyzed washcoat on the monolithic The products can be channeled to second-stage catalytic mem-
heat exchanger results in up to 10 times greater space veloc- brane reactor equipped with perm-selective membranes, which
ity (reduction in reactor size) compared to traditional processes can remove H2 from the product stream upon dehydrogenation.
by eliminating heat transfer resistance, which govern pelletized This inadvertently can lead to shift in equilibrium, thus allow-
packed bed reforming processes (Farrauto et al., 2007). For exam- ing for higher product conversion toward more olefin production.
ple, Polman et al. (1999) designed a steam reformer whereby the This concept is a good platform for process intensification and
inner reactor contain a series of plates with a metal monolithic overall improvements.
structure which alternate between corrugated foils and flat high- Despite the energy savings, environmental sustainability, com-
temperature steel. The monolith compartments were alternatively pact unit operation, and improved catalytic performance asso-
washcoated with combustion and steam reforming catalysts. The ciated with integrated catalytic membrane reactor concept for
steam reforming compartments receive the heat generated from CO2 -mediated dehydrogenation/reforming reactions, there are
the combustion compartment via the steel plates. however, some restrictions for industrial implementation. The
On the other hand, in order to maintain thermoneutrality of main barrier lies in the fundamental issue pertaining to stability
the reaction, much research has been carried out to improve the of the membrane in corrosive and reducing environment. Nev-
process efficiency as well as economic viability of the reactions ertheless, recent research developments show much focus on the
involving utilization of CO2 as an oxidant or as a reforming agent. design of chemically tolerant membranes. This is proven based
In order to achieve this, supply of oxygen provides exothermal on several successful studies on the implementation of integrated
energy, which can reduce the energy requirements (Jiang et al., catalytic membrane reactor systems for reactions such as CO2 -
2011). However, conventional oxygen supply via the pressure mediated reforming of methane (Slade et al., 2007;Yang et al., 2013;
swing adsorption (PSA) method requires high investment (Liang Kathiraser et al., 2013b). Substantial work, however, is required
and Caro, 2011). Besides, supply of oxygen externally in the form to enhance the robustness as well as inherent permeability char-
of molecular oxygen, gives rise to combustion of hydrocarbons acteristics of the membrane under the harsh chemical reaction
(especially at high quantities) and thus may not be particularly environment.
effective for improving selectivity.
One such solution to circumvent these issues is by providing CONCLUSION
oxygen supply in situ at controlled amounts. The catalytic mem- In recent years, the need to reduce escalating CO2 emissions to
brane reactor configuration combines a perm-selective membrane the atmosphere has become increasingly important. One method
that can not only reduce CO2 emission, but also can lead to pro- dehydrogenation catalyst for styrene production. Catal. Today doi:10.1016/j.
duction of valuable products is by utilizing CO2 as an oxidant. cattod.2014.10.029
Badstube, T., Papp, H., Kustrowski, P., and Dziembaj, R. (1998). Oxidative dehy-
Most of the reactions utilizing CO2 for high-temperature appli-
drogenation of ethylbenzene with carbon dioxide on alkali-promoted Fe/active
cations relate to the role of CO2 as an intermediary in saturated carbon catalysts. Catal. Lett. 55, 169–172. doi:10.1023/A:1019099332393
hydrocarbon conversion to olefins with release of hydrogen mol- Baek, J., Yun, H. J., Yun, D., Choi, Y., and Yi, J. (2012). Preparation of highly dispersed
ecule. The nature and properties of the catalysts such as redox or chromium oxide catalysts supported on mesoporous silica for the oxidative dehy-
acid–base play an important role in determining the catalytic activ- drogenation of propane using CO2 : insight into the nature of catalytically active
chromium sites. ACS Catal. 2, 1893–1903. doi:10.1021/cs300198u
ity as well as selectivity toward olefin production. Improvements
Bartholomew, C. H. (1984). Catalyst deactivation. Chem. Eng. 91, 96–112.
in the yield of olefins production remain a key factor, which Batiot-Dupeyrat, C., Valderrama, G., Meneses, A., Martinez, F., Barrault, J., and Tati-
requires much on-going research. On the other hand, utiliza- bouë, J. M. (2003). Pulse study of CO2 reforming of methane over LaNiO3 . Appl.
tion of CO2 for hydrocarbon reforming offer much potential Catal. A Gen. 248, 143–151. doi:10.1016/S0926-860X(03)00155-8
for hydrogen/syngas production. Syngas is an important build- Bellido, J. D. A., Tanabe, E. Y., and Assaf, E. M. (2009). Carbon dioxide reform-
ing of ethanol over Ni/Y2 O3 -ZrO2 catalysts. Appl. Catal. B 90, 485–488.
ing block for chemical production. Much efforts are emphasized doi:10.1016/j.apcatb.2009.04.009
toward synthesis of active and stable catalysts for CO2 reform- Bhattacharyya, A., and Chang, V. W. (1994). CO2 reforming of methane to syngas:
ing of methane (the simplest hydrocarbon molecule but requires deactivation behavior of nickel aluminate spinel catalysts. Stud. Surf. Sci. Catal.
greatest dissociation energy compared to other hydrocarbons). 88, 207–213. doi:10.1016/S0167-2991(08)62742-1
In this aspect, Ni is the most widely studied transition metal for Bitter, J. H., Seshan, K., and Lercher, J. A. (1999). Deactivation and coke accu-
mulation during CO2 /CH4 reforming over Pt catalysts. J. Catal. 183, 336–343.
reforming process in view of its wide availability and economic doi:10.1006/jcat.1999.2402
cost, compared to noble metals. Various improvements in cata- Blanchard, J., Oudghiri-Hassani, H., Abatzoglou, N., Jankhah, S., and Gitzhofer, F.
lyst structures have been made, with much effort directed toward (2008). Synthesis of nanocarbons via ethanol dry reforming over a carbon steel
synthesis of highly dispersed Ni nano-catalysts. However, besides catalyst. Chem. Eng. J. 143, 186–194. doi:10.1016/j.cej.2008.04.012
Blasco, T., Nieto, J. M. L., Dejoz, A., and Vazaquez, M. I. (1995). Influence of the
methane, much research efforts have been targeted toward reform-
acid-base character of supported vanadium catalysts on their catalytic prop-
ing of sustainable renewable sources such as ethanol and glycerol. erties for the oxidative dehydrogenation of n-butane. J. Catal. 157, 271–282.
Besides, syngas/hydrogen, reforming of these alcohols can be a doi:10.1006/jcat.1995.1291
potential source of CNFs, which have found a niche in the market. Botavina, M. A., Martra, G., Agafonov, Y. A., Gaidai, N. A., Nekrasov, N. V.,
Utilizing renewable resources pave the way toward utilizing CO2 Trushin, D. V., et al. (2008). Oxidative dehydrogenation of C3 –C4 paraffins in
the presence of CO2 over CrOx /SiO2 catalysts. Appl. Catal. A Gen. 347, 126–132.
in an environmentally sustainable manner in order to produce
doi:10.1016/j.apcata.2008.05.037
valuable energy/chemicals/products, which are much need in this Bradford, M. C. J., and Vannice, M. A. (1999). CO2 reforming of CH4 . Catal. Rev.
global age. Sci. Eng. 41, 1–42. doi:10.1081/CR-100101948
Budin, L.M., and Meyer, L.M. (2003). Oxidative Dehydrogenation of Alkanes to Olefins
ACKNOWLEDGMENTS Using an Oxide Surface. US Patent Application WO2003011444 A2.
The authors gratefully thank the National University of Singa- Burri, A., Jiang, N., Ji, M., Park, S. E., and Khalid, Y. (2013). Oxidative dehydrogena-
pore, NEA (NEA-ETRP 1002114, RP No. 279-000-333-490), and tion of ethylbenzene to styrene with CO2 over V2 O5 –Sb2 O5 –CeO2 /TiO2 –ZrO2
catalysts. Top. Catal. 56, 1724–1730. doi:10.1007/s11244-013-0108-0
NRF (NRF-POC 001-055, RP No. 279-000-397-281) for gener- Burri, D. R., Choi, K. M., Han, S. C., Burri, A., and Park, S. E. (2007). Selective conver-
ously supporting this work. Yasotha Kathiraser thanks Prof M. sion of ethylbenzene into styrene over K2 O/TiO2 -ZrO2 catalysts: unified effects
Aresta and Dr. Li Ziwei for their valuable input and discussion. of K2 O and CO2 . J. Mol. Catal. A Chem. 269, 58–63. doi:10.1016/j.molcata.2006.
12.021
REFERENCES Carja, G., Nakamura, R., Aida, T., and Niiyama, H. (2003). Mg–V–Al mixed oxides
Abatzoglou, N., Blanchard, J., Oudghiri-Hassani, H., Jankhah, S., and Gitzhofer, F. with mesoporous properties using layered double hydroxides as precursors:
(2006).“The use of catalytic reforming reactions for CO2 sequestration as carbon catalytic behavior for the process of ethylbenzene dehydrogenation to styrene
nanotubes,” in Proceedings of the 2006 IASME/WSEAS International Conference under a carbon dioxide flow. J. Catal. 218, 104–110. doi:10.1016/S0021-9517(03)
on Energy & Environmental Systems, (Chalkida: World Scientific and Engineering 00051-4
Academy and Society), 21–26. Caro, J., Caspary, K. J., Hamel, C., Hoting, B., Kolsch, P., Langanke, B., et al. (2007).
Adhikari, S., Fernando, S., To, S. D. F., Bricka, R. M., Steele, P. H., and Haryanto, A. Catalytic membrane reactors for partial oxidation using perovskite hollow fiber
(2008). Conversion of glycerol to hydrogen via a steam reforming process over membranes and for partial hydrogenation using a catalytic membrane contactor.
nickel catalysts. Energy Fuels 22, 1220–1226. doi:10.1021/ef700520f Ind. Eng. Chem. Res. 46, 2286–2294. doi:10.1021/ie0609620
Al-Muhaish, F.I., Ahmed, S., Bittencourt, R.C.P., Cardoso, M.J.B., and Souza, D. V.P. Castro, A. J. R., Soares, J. M., Filho, J. M., Oliveira, A. C., Edwin, A. C., and
(2015). Catalyst and Process for Thermo-Neutral Reforming of Liquid Hydrocar- Milet, R. C. (2013). Oxidative dehydrogenation of ethylbenzene with CO2
bons. US Patent Application US20150013225A1. for styrene production over porous iron-based catalysts. Fuel 108, 740–748.
Ansari, M. A., and Park, S. E. (2012). Carbon dioxide utilization as a soft oxidant and doi:10.1016/j.fuel.2013.02.019
promoter in catalysis. Energy Environ. Sci. 5, 9419–9437. doi:10.1039/c2ee22409g Cavani, F., Koutyrev, M., Trifiro, F., Bartolini, A., Ghisletti, D., Iezzi, R., et al.
Arena, F., Horrell, B. A., Cocke, D. L., Parmaliana, A., and Giordano, N. (1991). (1996). Chemical and physical characterization of alumina-supported chromia-
Magnesia-supported nickel catalysts I. Factors affecting the structure andmor- based catalysts and their activity in dehydrogenation of isobutene. J. Catal. 158,
phological properties. J. Catal. 132, 58–67. doi:10.1016/0021-9517(91)90246-Z 236–250. doi:10.1006/jcat.1996.0023
Aresta, M., Dibenedetto, A., and Angelini, A. (2013). The changing paradigm in CO2 Cheng, C. K., Foo, S. Y., and Adesina, A. A. (2012). Thermodynamic analysis of
utilization. J. CO2 Util. 3–4, 65–73. doi:10.1016/j.jcou.2013.08.001 glycerol dry reforming in the presence of CO2 or H2 as carbon gasifying agent.
Arnold, S.C., Koegler, J.H., Gaffney, A.M., Yeh, C.Y., and Song, R. (2014). Combined Int. J. Hydrogen Energy 37, 10101–10110. doi:10.1016/j.biortech.2008.11.021
Carbon Dioxide and Oxygen Process for Ethylbenzene Dehydrogenation to Styrene. Corthals, S., Van Nederkassel, J., Geboers, J., De Winne, H., Van Noyen, J., Moens,
US Patent US8765082 B2. B., et al. (2008). Influence of composition of MgAl2 O4 supported NiCeO2 ZrO2
Ba, H., Podila, S., Liu, Y., Mu, X., Nhut, J. M., Papaefthimiou, V., et al. (2014). Nan- catalysts on coke formation and catalyst stability for dry reforming of methane.
odiamond decorated few-layer graphene composite as an efficient metal-free Catal. Today 138, 28–32. doi:10.1016/j.cattod.2008.04.038

de Araujo, J. C. S., Souza, C. B. A., Oliveira, A. C., Freire, F. N. A., Ayala, A. P., and Jankhah, S., Abatzoglou, N., and Gitzhofer, F. (2008). Thermal and catalytic dry
Oliveira, A. C. (2010). Dehydrogenation of ethylbenzene with CO2 to produce reforming and cracking of ethanol for hydrogen and carbon nanofilaments’ pro-
styrene over Fe-containing ceramic composites. Appl. Catal. A Gen. 377, 55–63. duction. Int. J. Hydrogen Energy 33, 4769–4779. doi:10.1016/j.ijhydene.2008.06.
doi:10.1016/j.apcata.2010.01.016 058
de Lima, S. M., da Cruz, I. O., Jacobs, G., Davis, B. H., Mattos, L. V., and Noronha, F. Jiang, N., Han, D. S., and Park, S. E. (2009). Direct synthesis of mesoporous silicalite-
B. (2008). Steam reforming, partial oxidation, and oxidative steam reforming of 1 supported TiO2 –ZrO2 for the dehydrogenation of EB to styrene with CO2 .
ethanol over Pt/CeZrO2 catalyst. J. Catal. 257, 356–368. doi:10.1016/j.jcat.2008. Catal. Today 141, 344–348. doi:10.1016/j.cattod.2008.04.033
05.017 Jiang, Q., Faraji, S., Slade, D. A., and Stagg-Williams, S. M. (2011). Chapter 11- A
de Lima, S. M., da Silva, A. M., Jacobs, G., Davis, B. H., Mattosa, L. V., and Noronha, review of mixed ionic and electronic conducting ceramic membranes as oxy-
F. B. (2010). New approaches to improving catalyst stability over Pt/ceria during gen sources for high temperature reactions. Membr. Sci. Technol. 14, 235–273.
ethanol steam reforming: Sn addition and CO2 co-feeding. Appl. Catal. B 96, doi:10.1016/B978-0-444-53728-7.00011-2
387–398. doi:10.1016/j.apcatb.2010.02.036 Jimenez-Gonzalez, C., Boukha, Z., de Rivas, B., Gonzalez-Velasco, J. R., Gutierrez-
de Llobet, S., Pinilla, J. L., Moliner, R., and Suelves, I. (2015). Effect of the Ortiz, J. I., and Lopez-Fonseca, R. (2015). Behaviour of nickel-alumina spinel
synthesis conditions of Ni/Al2 O3 catalysts on the biogas decomposition to (NiAl2 O4 ) catalysts for isooctane steam reforming. Int. J. Hydrogen Energy
produce H2 -rich gas and carbon nanofibers. Appl. Catal. B 165, 457–465. doi:10.1016/j.ijhydene.2015.01.064
doi:10.1016/j.apcatb.2014.10.014 Kale, G. R., and Kulkarni, B. D. (2010). Thermodynamic analysis of dry autothermal
Deng, S., Li, H., Li, S., and Zhang, Y. (2007). Activity and characterization of reforming of glycerol. Fuel Process. Technol. 91, 520–530. doi:10.1016/j.fuproc.
modified Cr2 O3 /ZrO2 nano-composite catalysts for oxidative dehydrogena- 2009.12.015
tion of ethane to ethylene with CO2 . J. Mol. Catal. A Chem. 268, 169–175. Kathiraser, Y., Thitsartarn, W., Sutthiumporn, K., and Kawi, S. (2013a). Inverse
doi:10.1016/j.molcata.2006.12.033 NiAl2 O4 on LaAlO3 –Al2 O3 : unique catalytic structure for stable CO2 reforming
Dury, F., Gaigneaux, E. M., and Ruiz, P. (2003a). The active role of CO2 at of methane. J. Phys. Chem. C 117, 8120–8130. doi:10.1021/jp401855x
low temperature in oxidation processes: the case of the oxidative dehydro- Kathiraser, Y., Wang, Z., and Kawi, S. (2013b). Oxidative CO2 reforming of methane
genation of propane on NiMoO4 catalysts. Appl. Catal. A Gen. 242, 187–203. in La0.6 Sr0.4 Co0.8 Ga0.2 O3-δ (LSCG) hollow fiber membrane. Environ. Sci. Tech-
doi:10.1016/S0926-860X(02)00516-1 nol. 47, 14510–14517. doi:10.1021/es403158k
Dury, F., Centeno, M. A., Gaigneaux, E. M., and Ruiz, P. (2003b). An attempt to Khavarian, M., Chai, S. P., and Mohamed, A. R. (2014). Direct use of as-synthesized
explain the role of CO2 and N2 O as gas dopes in the feed in the oxidative dehy- multi-walled carbon nanotubes for carbon dioxide reforming of methane for
drogenation of propane. Catal. Today 81, 95–105. doi:10.1016/S0920-5861(03) producing synthesis gas. Chem. Eng. J. 257, 200–208. doi:10.1016/j.cej.2014.05.
00120-2 079
Ebshish, A., Yaakob, Z., Taufiq-Yap, Y. H., Bshish, A., and Tasirin, S. M. (2012). Lee, D. W., Yu, C. Y., and Lee, K. H. (2008). Study on hydrothermal stability and
Review of hydrogen production via glycerol reforming. Proc I Mech E Part A J catalytic activity of nanosphere-walled mesoporous silica. J. Phys. Chem. C 112,
Power Energy 226, 1060–1075. doi:10.1177/0957650912464624 5136–5140. doi:10.1021/jp712051p
Erdöhelyi, A., Cserényi, J., Papp, E., and Solymosi, F. (1994). Catalytic reaction of Lee, H. C., Siew, K. W., Khan, M. R., Chin, S. Y., Gimbun, J., and Cheng, C. K. (2014).
methane with carbon dioxide over supported palladium. Appl. Catal. A Gen. 108, Catalytic performance of cement clinker supported nickel catalyst in glycerol dry
205–219. doi:10.1016/0926-860X(94)85071-2 reforming. J. Energy Chem. 23, 645–656. doi:10.1016/S2095-4956(14)60196-0
Fan, M.-S., Abdullah, A. Z., and Bhatia, S. (2009). Catalytic technology for car- Lezla, O., Bordes, E., Courtine, P., and Hecquet, G. (1997). Synergetic effects in
bon dioxide reforming of methane to synthesis gas. ChemCatChem 1, 192–208. the Ni-Mo-O system: influence of preparation on catalytic performance in the
doi:10.1002/cctc.200900025 oxidative dehydrogenation of propane. J. Catal. 170, 346–356. doi:10.1006/jcat.
Farrauto, R. J., Liu, Y., Ruettinger, W., Ilinich, O., Shore, L., and Giroux, T. 1997.1759
(2007). Precious metal catalysts supported on ceramic and metal monolithic Li, W., Li, X., and Feng, J. (2009). Behaviors of V-doped titanium mixed oxides
structures for the hydrogen economy. Catal. Rev. 49, 141–196. doi:10.1080/ in the catalytic dehydrogenation of ethylbenzene. Catal. Lett. 130, 575–582.
01614940701220496 doi:10.1007/s10562-009-9971-5
Fontananova, E., and Drioli, E. (2010). Catalytic membranes and membrane reac- Li, Z., Mo, L., Kathiraser, Y., and Kawi, S. (2014a). Yolk–satellite–shell structured Ni–
tors. Compr. Membr. Sci. Eng. 3, 109–133. doi:10.1016/B978-0-08-093250-7. Yolk@Ni@SiO2 nanocomposite: superb catalyst toward methane CO2 reforming
00022-0 reaction. ACS Catal. 4, 1526–1536. doi:10.1021/cs401027p
Gallego, G. S., Mondrago, F., Barrault, J., Tatibouet, J. M., and Batiot-Dupeyrat, C. Li, Z., Kathiraser, Y., and Kawi, S. (2014b). Facile synthesis of high surface area yolk–
(2006). CO2 reforming of CH4 over La–Ni based perovskite precursors. Appl. shell Ni@Ni embedded SiO2 via Ni phyllosilicate with enhanced performance
Catal. A Gen. 311, 164–171. doi:10.1016/j.apcata.2006.06.024 for CO2 reforming of CH4 . ChemCatChem 7, 160–168. doi:10.1002/cctc.
Gallego, G. S., Mondragón, F., Tatibouët, J. M., Barrault, J., and Batiot-Dupeyrat, 201402673
C. (2008). Carbon dioxide reforming of methane over La2 NiO4 as catalyst Li, Z., Kathiraser, Y., Ashok, J., Oemar, U., and Kawi, S. (2014c). Simultane-
precursor—Characterization of carbon deposition. Catal. Today 13, 200–209. ous Tuning Porosity and Basicity of Nickel@Nickel–Magnesium Phyllosilicate
doi:10.1016/j.cattod.2007.12.075 Core–Shell Catalysts for CO2 Reforming of CH4 . Langmuir 30, 14694–14705.
Gao, J., Hou, Z., Lou, H., and Zheng, X. (2011). “Dry (CO2 ) reforming, Chapter 7,” doi:10.1021/la503340s
in Fuel Cells: Technologies for fuel processing, eds D. Shekhawat, J. J. Spivey, and Liang, F., and Caro, J. (2011). “Perovskite membranes for high temperature oxy-
D. A. Berry (Oxford: Elsevier B. V.), 191–221. doi:10.1016/B978-0-444-53563- gen separation,” in Membrane Engineering for the Treatment of Gases, Volume 2:
4.10007-0 Gas-Separation Problems Combined with Membrane Reactors, eds E. Drioli and
Gaur, S., Pakhare, D., Wu, H., Haynes, D. J., and Spivey, J. J. (2012). CO2 reform- G. Barbieri (Cambridge, UK: Royal Society of Chemistry), 192–221.
ing of CH4 over Ru-substituted pyrochlore catalysts: effects of temperature and Liu, H., Zhang, Z., Li, H., and Huang, Q. (2011). Intrinsic kinetics of oxidative dehy-
reactant feed ratio. Energy Fuels 26, 1989–1998. doi:10.1021/ef300158y drogenation of propane in the presence of CO2 over Cr/MSU-1 catalyst. J. Nat.
Ge, S., Liu, C., Zhang, S., and Li, Z. (2003). Effect of carbon dioxide on the reaction Gas Chem. 20, 311–317. doi:10.1016/S1003-9953(10)60180-6
performance of oxidative dehydrogenation of n-butane over V-Mg-O catalyst. Liu, L., and Li, H. (2006). A comparative study on catalytic performances of
Chem. Eng. J. 94, 121–126. doi:10.1016/S1385-8947(03)00023-8 chromium incorporated and supported mesoporous MSU-x catalysts for the
Han, S., Jin, L., Martenak, D.J., and Suib, S.L. (2010). Improved Process for the Oxida- oxidehydrogenation of ethane to ethylene with carbon dioxide. Catal. Today
tive Dehydrogenation of Ethane. European Patent Application EP2165997 A1. 115, 235–241. doi:10.1016/j.cattod.2006.02.040
Hu, X., and Lu, G. (2009). Syngas production by CO2 reforming of ethanol over Liu, L., Li, H., and Zhang, Y. (2007). Mesoporous silica-supported chromium cata-
Ni/Al2 O3 catalyst. Catal. Commun. 10, 1633–1637. doi:10.1016/j.catcom.2009. lyst: characterization and excellent performance in dehydrogenation of propane
04.030 to propylene with carbon dioxide. Catal. Commun. 8, 565–570. doi:10.1016/j.
Irún, O., Sadosche, S. A., Lasobras, J., Soler, J., Francés, E., Herguido, J., et al. (2013). catcom.2006.08.005
Catalysts for the production of styrene from ethylbenzene: redox and deactiva- Liu, Y. M., Cao, Y., Yi, N., Feng, W. L., Dai, W. L., Yan, S. R., et al. (2004). Vana-
tion study. Catal. Today 203, 53–59. doi:10.1016/j.cattod.2012.07.019 dium oxide supported on mesoporous SBA-15 as highly selective catalysts in the
oxidative dehydrogenation of propane. J. Catal. 224, 417–428. doi:10.1016/j.jcat. Park, S. E., and Ansari, M. B. (2013). “Carbon dioxide as soft oxidant and promoter
2004.03.010 in oxidation catalysis,” in New and Future Developments in Catalysis, ed. S. L. Suib
Mark, M. F., and Maier, W. F. (1996). CO2 -reforming of methane on supported Rh (Oxford, UK: Elsevier), 481–499. doi:10.1016/B978-0-444-53882-6.00017-6
and Ir catalysts. J. Catal. 164, 122–130. doi:10.1006/jcat.1996.0368 Park, S.E., Chang, J.S., and Park, M.S. (2005). Method for Catalytic Dehydrogenation
McCoy, S. T., and Rubin, E. S. (2008). An engineering-economic model of pipeline of Hydrocarbons using Carbon Dioxide as a Soft Oxidant. US Patent 6958427 B2
transport of CO2 with application to carbon capture and storage. Int. J. Green- Pena, M. A., and Fierro, J. L. G. (2001). Chemical structures and performance of
house Gas Control 2, 219–229. doi:10.1016/S1750-5836(07)00119-3 perovskite oxides. Chem. Rev. 101, 1981–2018. doi:10.1021/cr980129f
Michorczyk, P., Pietrzyk, P., and Ogonowski, J. (2012). Preparation and characteri- Polman, E. A., Der Kinderen, J. M., and Thuis, F. M. A. (1999). Novel compact steam
zation of SBA-1–supported chromium oxide catalysts for CO2 assisted dehydro- reformer for fuel cells with heat generation by catalytic combustion augmented
genation of propane. Microporous Mesoporous Mater. 161, 56–66. doi:10.1016/j. by induction heating. Catal. Today 47, 347–351. doi:10.1016/S0920-5861(98)
micromeso.2012.05.011 00316-2
Mimura, N., Okamoto, M., Yamashita, H., Oyama, S. T., and Murata, K. (2006). Postole, G., Chowdhury, B., Pinki, K., Banerji, J., and Auroux, A. (2010). Knoevenagel
Oxidative dehydrogenation of ethane over Cr/ZSM-5 catalysts using CO2 as an condensation reaction over acid–base bifunctional nanocrystalline Cex Zr1-x O2
oxidant. J. Phys. Chem. B 110, 21764–21770. doi:10.1021/jp061966l solid solutions. J. Catal. 269, 110–121. doi:10.1016/j.jcat.2009.10.022
Mimura, N., and Saito, M. (2000). Dehydrogenation of ethylbenzene to styrene Pramod, C. V., Raghavendra, C., Reddy, K. H. P., Babu, G. V. R., Rao, K. S. R.,
over Fe2 O3 /Al2 O3 catalysts in the presence of carbon dioxide. Catal. Today 55, and Raju, B. D. (2014). Concept and progress in coupling of dehydrogena-
173–178. doi:10.1016/S0920-5861(99)00236-9 tion and hydrogenation reactions through catalysts. J. Chem. Sci. 126, 311–317.
Mo, L., Leong, K. K. M., and Kawi, S. (2014). A highly dispersed and anti- doi:10.1007/s12039-014-0576-1
coking Ni–La2 O3 /SiO2 catalyst for syngas production from dry carbon Puolakka, K. J., and Krause, A. O. I. (2007). Combined CO2 reforming and partial
dioxide reforming of methane. Catal. Sci. Technol. 4, 2107–2114. doi:10.1039/ oxidation of fuel compounds. Catal. Lett. 116, 87–93. doi:10.1007/s10562-007-
c3cy00869j 9112-y
Moradi, G. R., Rahmanzadeh, M., and Khosravian, F. (2014). The effects of partial Qiao, A., Kalevaru, V. N., Radnik, J., Düvel, A., Heitjans, P., Hari Kumar, A. S., et al.
substitution of Ni by Zn in LaNiO3 perovskite catalyst for methane dry reform- (2014). Oxidative dehydrogenation of ethane to ethylene over V2 O5 /Al2 O3 cat-
ing. J. CO2 Util. 6, 7–11. doi:10.1016/j.jcou.2014.02.001 alysts: effect of source of alumina on the catalytic performance. Ind. Eng. Chem.
Nagaoka, K., Seshan, K., Aika, K., and Lercher, J. A. (2001). Carbon deposition dur- Res. 53, 18711–18721. doi:10.1021/ie5008344
ing carbon dioxide reforming of methane—comparison between Pt/Al2 O3 and Qiao, Y., Miao, C., Yue, Y., Xie, Z., Yang, W., Hua, W., et al. (2009). Vanadium
Pt/ZrO2 . J. Catal. 197, 34–42. doi:10.1006/jcat.2000.3062 oxide supported on mesoporous MCM-41 as new catalysts for dehydrogena-
Nakagawa, K., Kajita, C., Ikenaga, N. O., Gamo, M. N., Ando, T., and Suzuki, T. tion of ethylbenzene with CO2 . Microporous Mesoporous Mater. 119, 150–157.
(2003). Dehydrogenation of light alkanes over oxidized diamond-supported cat- doi:10.1016/j.micromeso.2008.10.010
alysts in the presence of carbon dioxide. Catal. Today 84, 149–157. doi:10.1016/ Raju, G., Reddy, B. M., Abhishek, B., Mo, Y. H., and Park, S. E. (2012). Synthesis of
S0920-5861(03)00268-2 C4 olefins from n-butane over a novel VOx /SnO2 –ZrO2 catalyst using CO2 as
Ni, J., Chen, L., Lin, J., and Kawi, S. (2012). Carbon deposition on borated alumina soft oxidant. Appl. Catal. A Gen. 423–424. doi:10.1016/j.apcata.2012.02.040
supported nano-sized Ni catalysts for dry reforming of CH4 . Nano Energy 1, Raju, G., Reddy, B. M., and Park, S. E. (2014). CO2 promoted oxidative dehydro-
674–686. doi:10.1016/j.nanoen.2012.07.011 genation of n-butane over VOx /MO2 –ZrO2 (M Ce or Ti) catalysts. J. CO2 Util.
Ni, J., Chen, L., Lin, J., Schreyer, M. K., Wang, Z., and Kawi, S. (2013). High per- 5, 41–46. doi:10.1016/j.jcou.2013.12.003
formance of MgeLa mixed oxides supported Ni catalysts for dry reforming of Rangel, M. D. C., Monteiro, A. P. D. M., Oportus, M., Reyes, P., RAMOS, M. D.
methane: the effect of crystal structure. Int. J. Hydrogen Energy 38, 13631–13642. S., and Lima, S. B. (2012). “Ethylbenzene dehydrogenation in the presence of
doi:10.1016/j.ijhydene.2013.08.041 carbon dioxide over metal oxides,” in Greenhouse Gases-Capturing, Utilization
Obradovic, A., Likozar, B., and Levec, J. (2013). Catalytic surface development of and Reduction, ed. G. Liu (Rijeka: INTECH Open Access Publisher), 117–136.
novel nickel plate catalyst with combined thermally annealed platinum and Rao, K. N., Reddy, B. M., Abishek, B., Seo, Y. H., Jiang, N., and Park, S. E. (2009).
alumina coatings for steam methane reforming. Int. J. Hydrogen Energy. 38, Effect of ceria on the structure and catalytic activity of V2 O5 /TiO2 –ZrO2 for
1419–1429. doi:10.1016/j.ijhydene.2012.11.015 oxidehydrogenation of ethylbenzene to styrene utilizing CO2 as soft oxidant.
Oemar, U., Hidajat, K., and Kawi, S. (2011). Role of catalyst support over PdO–NiO Appl. Catal. B 91, 649–656. doi:10.1016/j.apcatb.2009.07.003
catalysts on catalyst activity and stability for oxy-CO2 reforming of methane. Reddy, B. M., Jin, H., Han, D. S., and Park, S. E. (2008). Oxidative dehydrogena-
Appl. Catal. A Gen. 402, 176–187. doi:10.1016/j.apcata.2011.06.002 tion of ethylbenzene to styrene with carbon dioxide over Fe2 O3 /TiO2 –ZrO2
Olah, G.A., and Prakash, G.K.S. (2013). Conversion of Carbon Dioxide to Methanol catalyst: influence of chloride. Catal. Lett. 124, 357–363. doi:10.1007/s10562-
Using Bi-Reforming of Methane or Natural Gas. US Patent US8440729 B2. 008-9475-8
Oliveira-Vigier, K. D., Abatzoglou, N., and Gitzhofer, F. (2005). Dry-reforming of Reddy, G. K., Boolchand, P., and Smirniotis, P. G. (2012). Unexpected behavior of
ethanol in the presence of a 316 stainless steel catalyst. Can. J. Chem. Eng. 83, copper in modified ferrites during high temperature WGS reaction-aspects of
978–984. doi:10.1002/cjce.5450830607 Fe3+ ↔ Fe2+ redox chemistry from Mössbauer and XPS studies. J. Phys. Chem.
Pak, S., Qiu, P., and Lunsford, J. H. (1998). Elementary reactions in the oxidative C 116, 11019–11031. doi:10.1021/jp301090d
coupling of methane over Mn/Na2 WO4 /SiO2 and Mn/Na2 WO4 /MgO catalysts. Rezaei, M., Alavi, S. M., Sahebdelfar, S., and Yan, Z. F. (2006). Syngas production
J. Catal. 179, 222–230. doi:10.1006/jcat.1998.2228 by methane reforming with carbon dioxide on noble metal catalysts. J. Nat. Gas
Pakhare, D., Schwartz, V., Abdelsayed, V., Haynes, D., Shekhawat, D., Poston, J., et al. Chem. 15, 327–334. doi:10.1016/S1003-9953(07)60014-0
(2014). Kinetic and mechanistic study of dry (CO2 ) reforming of methane over Rostrup-Nielsen, J. R., Sehested, J., and Norskov, J. K. (2002). Hydrogen and syn-
Rh-substituted La2 Zr2 O7 pyrochlores. J. Catal. 316, 78–92. doi:10.1016/j.jcat. thesis gas by steam- and CO2 reforming. Adv. Catal. 47, 65–139. doi:10.1016/
2014.04.023 S0360-0564(02)47006-X
Pakhare, D., Shaw, C., Haynes, D., Shekhawat, D., and Spivey, J. (2013a). Effect of Ruckenstein, E., and Hu, Y. H. (1996). Role of support in CO2 reforming of CH4 to
reaction temperature on activity of Pt- and Ru-substituted lanthanum zirconate syngas over Ni catalysts. J. Catal. 162, 230–238. doi:10.1006/jcat.1996.0280
pyrochlores (La2 Zr2 O7 ) for dry (CO2 ) reforming of methane (DRM). J. CO 2 Sankar, M., Dimitratos, N., Miedziak, P. J., Wells, P. P., Kiely, C. J., and Hutchings,
Util. 1, 37–42. doi:10.1016/j.jcou.2013.04.001 G. J. (2012). Designing bimetallic catalysts for a green and sustainable future.
Pakhare, D., Wu, H., Narendra, S., Abdelsayed, V., Haynes, D., Shekhawat, D., et al. Chem. Soc. Rev. 41, 8099–8139. doi:10.1039/c2cs35296f
(2013b). Characterization and activity study of the Rh-substituted pyrochlores Sattler, J. J. H. B., Ruiz-Martinez, J., Santillan-Jimenez, E., and Weckhuysen, B. M.
for CO2 (dry) reforming of CH4 . Appl. Petrochem. Res. 3, 117–129. doi:10.1007/ (2014). Catalytic dehydrogenation of light alkanes on metals and metal oxides.
s13203-013-0042-x Chem. Rev. 114, 10613–10653. doi:10.1021/cr5002436
Pan, Y. X., Kuai, P., Liu, Y., Ge, Q., and Liu, C. J. (2010). Promotion effects of Ga2 O3 Schwint, K.J., and Wilcox, R.J. (2009). Styrene Monomer Process Based on Oxidative
on CO2 adsorption and conversion over a SiO2 -supported Ni catalyst. Energy Dehydrogenation of Ethylbenzene Using CO2 as a Soft Oxidant. Patent Application
Environ. Sci. 3, 1322–1325. doi:10.1039/c0ee00149j CA2723873A1.

Siew, K. W., Lee, H. C., Gimbun, J., and Cheng, C. K. (2014). Production of CO-rich Van, D.B. P.J., Kramer, G.J., Murphy, A., and Vos, E.J. (2006). Process for Steam and/or
hydrogen gas from glycerol dry reforming over La-promoted Ni/Al2 O3 catalyst. CO2 Reforming of a Hydrocarbonaceous Feedstock. European Patent Application
Int. J. Hydrogen Energy 39, 6927–6936. doi:10.1016/j.ijhydene.2014.02.059 WO2006045744 A1.
Siew, K. W., Lee, H. C., Gimbun, J., Chin, S. Y., Khan, M. R., Taufiq-Yap, Y. H., Vasant, R. C., and Kartick, C. M. (2006). CO2 reforming of methane combined
et al. (2015). Syngas production from glycerol-dry(CO2 ) reforming over La- with steam reforming or partial oxidation of methane to syngas over NdCoO3
promoted Ni/Al2 O3 catalyst. Renew. Energy 74, 441–447. doi:10.1016/j.renene. perovskite-type mixed metal-oxide catalyst. Appl. Energy. 83, 1024–1032. doi:10.
2014.08.048 1016/j.apenergy.2005.09.008
Slade, D. A., Duncan, A. M., Nordheden, K. J., and Stagg-Williams, S. M. (2007). Vilarrasa, V., Silva, O., Carrera, J., and Olivella, S. (2013). Liquid CO2 injection for
Mixed-conducting oxygen permeable ceramic membranes for the carbon diox- geological storage in deep saline aquifers. Int. J. Greenhouse Gas Control. 14,
ide reforming of methane. Green Chem. 9, 577–581. doi:10.1039/b614232j 84–96. doi:10.1016/j.ijggc.2013.01.015
Smart, S., Liu, S., Serra, J. M., Basile, A., and da Costa, J. C. D. (2014). “Perovskite Wang, H., Tablet, C., Schiestel, T., and Caro, J. (2006). Hollow fiber membrane
membrane reactors: fundamentals and applications for oxygen production, syn- reactors for the oxidative activation of ethane. Catal. Today 118, 98–103.
gas production and hydrogen processing,” in Membranes for Clean and Renew- doi:10.1016/j.cattod.2005.11.093
able Power Applications, eds A. Gugliuzza and A. Basile (Cambridge: Woodhead Wang, H., Zhang, J., and Dalai, A.K. (2011). Catalyst for Production of Synthesis Gas.
Publishing Limited), 182–217. US Patent US7985710 B2.
Smith, R.S. (2008). Simultaneous Dehydrogenation of Ethylbenzene and Ethane in the Wang, Q., Li, X., Li, W., and Feng, J. (2014a). Promoting effect of Fe in oxida-
Presence of CO2 or Steam. Patent Application CA2561986 A1. tive dehydrogenation of ethylbenzene to styrene with CO2 (I) preparation and
Solsona, B., Blasco, T., Nieto, J. M. L., Peña, M. L., Rey, F., and Vidal-Moya, A. performance of Ce1 - x Fex O2 catalyst. Catal. Commun. 50, 21–24. doi:10.1016/j.
(2001). Vanadium oxide supported on mesoporous MCM-41 as selective cat- catcom.2014.02.014
alysts in the oxidative dehydrogenation of alkanes. J. Catal. 203, 443–452. Wang, Z., Cao, X. M., Zhu, J., and Hu, P. (2014b). Activity and coke forma-
doi:10.1006/jcat.2001.3326 tion of nickel and nickel carbide in dry reforming: a deactivation scheme
Solymosi, F., and Nemeth, R. (1999). The oxidative dehydrogenation of ethane from density functional theory. J. Catal. 311, 469–480. doi:10.1016/j.jcat.2013.
with CO2 over Mo2 C/SiO2 catalyst. Catal. Lett. 62, 197–200. doi:10.1023/A: 12.015
1019027912597 Wang, W. (2011). Hydrogen production via dry reforming of butanol: thermody-
Solymosi, F., Nemeth, R., and Oszko, A. (2001). The oxidative dehydrogenation of namic analysis. Fuel 90, 1681–1688. doi:10.1016/j.fuel.2010.11.001
propane with CO2 over supported Mo2 C catalyst. Stud. Surf. Sci. Catal. 136, Wang, X., Li, M., Wang, M., Wang, S., Li, S., Wang, S., et al. (2009). Thermodynamic
339–344. doi:10.1016/S0167-2991(01)80326-8 analysis of glycerol dry reforming for hydrogen and synthesis gas production.
Souza, M. M. V. M., Aranda, D. A. G., and Schmal, M. (2001). Reforming of methane Fuel 88, 2148–2153. doi:10.1016/j.fuel.2009.01.015
with carbon dioxide over Pt/ZrO2 /Al2 O3 catalysts. J. Catal. 204, 498–511. Wu, X., and Kawi, S. (2009). Active and stable catalyst for CO2 reforming
doi:10.1006/jcat.2001.3398 of ethanol to hydrogen. Catal. Today 148, 251–259. doi:10.1016/j.cattod.2009.
Souza, M. M. V. M., Aranda, D. A. G., and Schmal, M. (2002). Coke formation on 08.006
Pt/ZrO2 /Al2 O3 catalysts during CH4 reforming with CO2 . Ind. Eng. Chem. Res. Yang, N. T., Kathiraser, Y., and Kawi, S. (2013). La0.6 Sr0.4 Co0.8 Ni0.2 O3-δ hollow fiber
41, 4681–4685. doi:10.1021/ie010970a membrane reactor: integrated oxygen separation–CO2 reforming of methane
Stankiewicz, A. I., and Moulijn, J. A. (2000). Process intensification: transforming reaction for hydrogen production. Int. J. Hydrogen Energry. 38, 4483–4491.
chemical engineering. Chem. Eng. Prog. 96, 22–34. doi:10.1016/j.ijhydene.2013.01.073
Styring, P., and Armstrong, K. (2011). Catalytic carbon dioxide conversions to value Yokota, S., Okumura, K., and Niwa, M. (2002). Support effect of metal oxide
added chemicals. Chimica Oggi Chem. Today 29, 34–37. on Rh catalysts in the CH4 -CO2 reforming reaction. Catal. Lett. 84, 131–134.
Sutthiumporn, K., and Kawi, S. (2011). Promotional effect of alkaline earth over Ni– doi:10.1023/A:1021097206196
La2 O3 catalyst for CO2 reforming of CH4 : role of surface oxygen species on H2 Zawadzki, A., Bellido, J. D. A., Lucrédio, A. F., and Assaf, E. M. (2014). Dry reforming
production and carbon suppression. Int. J. Hydrogen Energy 36, 14435–14446. of ethanol over supported Ni catalysts prepared by impregnation with methano-
doi:10.1016/j.ijhydene.2011.08.022 lic solution. Fuel Process. Technol. 128, 432–440. doi:10.1016/j.fuproc.2014.08.
Sutthiumporn, K., Maneerung, T., Kathiraser, Y., and Kawi, S. (2012). CO2 dry 006
reforming of methane over La0.8 Sr0.2 Ni0.8 M0.2 O3 perovskite (M Bi, Co, Cr, Cu, Zhang, B. C., Tang, X. L., Li, Y., Xu, Y., and Shen, W. J. (2007a). Hydrogen produc-
Fe): roles of lattice oxygen on C–H activation and carbon suppression. Int. J. tion from steam reforming of ethanol and glycerol over ceria-supported metal
Hydrogen Energy 37, 11195–11207. doi:10.1016/j.ijhydene.2012.04.059 catalysts. Int. J. Hydrogen Energy 32, 2367–2373. doi:10.1016/j.ijhydene.2006.11.
Takehira, K., Ohishi,Y., Shishido, T., Kawabata, T., Takaki, K., Zhang, Q., et al. (2004). 003
Behavior of active sites on Cr-MCM-41 catalysts during the dehydrogenation of Zhang, J., Wang, H., and Dalai, A. K. (2007b). Development of stable bimetal-
propane with CO2 . J. Catal. 224, 404–416. doi:10.1016/j.jcat.2004.03.014 lic catalysts for carbon dioxide reforming of methane. J. Catal. 249, 300–310.
Tonkovich, A. L. Y., Yang, B., Perry, S., Fitzgerald, S. P., and Wang, Y. (2007). doi:10.1016/j.jcat.2007.05.004
From seconds to milliseconds to microseconds through tailored microchan- Zhang, J., Wang, H., and Dalai, A. K. (2008). Effects of metal content on activity and
nel reactor designs of a steam methane reformer. Catal. Today 120, 21–29. stability of Ni-Co bimetallic catalysts for CO2 reforming of CH4 . Appl. Catal. A
doi:10.1016/j.cattod.2006.07.022 Gen. 339, 121–129. doi:10.1016/j.apcata.2008.01.027
Tsiakarasa, P., and Demin, A. (2001). Thermodynamic analysis of a solid oxide fuel Zhang, Q., Uchaker, E., Candelariaz, S. L., and Cao, G. (2013). Nanomaterials for
cell system fuelled by ethanol. J. Power Sources 102, 210–217. doi:10.1016/S0378- energy conversion and storage. Chem. Soc. Rev. 42, 3128–3171. doi:10.1039/
7753(01)00803-5 c3cs00009e
Urlan, F., Marcu, I. C., and Sandulescu, I. (2008). Oxidative dehydrogenation of n- Zhang, X., Yue, Y., and Gao, Z. (2002). Chromium oxide supported on mesoporous
butane over titanium pyrophosphate catalysts in the presence of carbon dioxide. SBA-15 as propane dehydrogenation and oxidative dehydrogenation catalysts.
Catal. Commun. 9, 2403–2406. doi:10.1016/j.catcom.2008.05.038 Catal. Lett. 83, 19–25. doi:10.1023/A:1021069510797
Valderrama, G., Kiennemann, A., and Goldwasser, M. R. (2010). La-Sr-Ni-Co-O Zhang, Z. L., Tsipouriari, V. A., Efstathiou, A. M., and Verykios, X. E. (1996).
based perovskite-type solid solutions as catalyst precursors in the CO2 reform- Reforming of methane with carbon dioxide to synthesis gas over supported
ing of methane. J. Power Sources 195, 1765–1771. doi:10.1016/j.jpowsour.2009. rhodium catalysts: I. Effects of support and metal crystallite size on reaction
10.004 activity and deactivation characteristics. J. Catal. 158, 51–63. doi:10.1006/jcat.
Valensa, J. (2009). A Mixed-Dimensionality Modeling Approach for Interaction of 1996.0005
Heterogeneous Steam Reforming Reactions and Heat Transfer. Masters Theses, Zhao, S., and Wagner, J.P. (2004). Nickel-Catalyst for Syngas Generation by Mixed
Marquette University, Milwaukee, WI. Reforming Using CO2 and Steam. US Patent Application WO2004011138 A1.
Valliyappan, T., Bakhshi, N. N., and Dalai, A. K. (2008). Pyrolysis of glycerol Zhao, X., and Wang, X. (2006). Oxidative dehydrogenation of ethane to ethyl-
for the production of hydrogen or syngas. Bioresour. Technol. 99, 4476–4483. ene by carbon dioxide over Cr/TS-1 catalysts. Catal. Commun. 7, 633–638.
doi:10.1016/j.biortech.2007.08.069 doi:10.1016/j.catcom.2006.02.005
Zhu, X., Huo, P., Zhang, Y., Cheng, D., and Liu, C. (2008). Structure and reactivity Citation: Kawi S and Kathiraser Y (2015) CO2 as an oxidant for high-temperature
of plasma treated Ni/Al2 O3 catalyst for CO2 reforming of methane. Appl. Catal. reactions. Front. Energy Res. 3:13. doi: 10.3389/fenrg.2015.00013
B 81, 132–140. doi:10.1016/j.apcatb.2007.11.042 This article was submitted to Carbon Capture, Storage, and Utilization, a section of the
journal Frontiers in Energy Research.
Copyright © 2015 Kawi and Kathiraser. This is an open-access article distributed under
Conflict of Interest Statement: The authors declare that the research was conducted the terms of the Creative Commons Attribution License (CC BY). The use, distribution
in the absence of any commercial or financial relationships that could be construed or reproduction in other forums is permitted, provided the original author(s) or licensor
as a potential conflict of interest. are credited and that the original publication in this journal is cited, in accordance with
accepted academic practice. No use, distribution or reproduction is permitted which
Received: 14 January 2015; accepted: 03 March 2015; published online: 18 March 2015. does not comply with these terms.

High Temperature Co2 Reactions

Uploaded by

Copyright:

Available Formats

High Temperature Co2 Reactions

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

High Temperature Co2 Reactions

Uploaded by

Copyright:

Available Formats

REVIEW ARTICLE

CO2 as an oxidant for high-temperature reactions

INTRODUCTION of this review is to focus on the utilization of CO2 as an oxidant

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 1

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 3

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 5

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 7

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 9

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 11

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 13

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 15

www.frontiersin.org March 2015 | Volume 3 | Article 13 | 17

You might also like