Professional Documents
Culture Documents
A Review of Dry (CO2) Reforming of Methane Over
A Review of Dry (CO2) Reforming of Methane Over
Dry (CO2) reforming of methane (DRM) is a well-studied reaction that is of both scientific and industrial
importance. This reaction produces syngas that can be used to produce a wide range of products, such
as higher alkanes and oxygenates by means of Fischer–Tropsch synthesis. DRM is inevitably accompa-
nied by deactivation due to carbon deposition. DRM is also a highly endothermic reaction and requires
operating temperatures of 800–1000 1C to attain high equilibrium conversion of CH4 and CO2 to H2
and CO and to minimize the thermodynamic driving force for carbon deposition. The most widely used
catalysts for DRM are based on Ni. However, many of these catalysts undergo severe deactivation due
to carbon deposition. Noble metals have also been studied and are typically found to be much more
resistant to carbon deposition than Ni catalysts, but are generally uneconomical. Noble metals can also
be used to promote the Ni catalysts in order to increase their resistance to deactivation. In order to
Received 2nd November 2013 design catalysts that minimize deactivation, it is necessary to understand the elementary steps involved
DOI: 10.1039/c3cs60395d in the activation and conversion of CH4 and CO2. This review will cover DRM literature for catalysts
based on Rh, Ru, Pt, and Pd metals. This includes the effect of these noble metals on the kinetics,
www.rsc.org/csr mechanism and deactivation of these catalysts.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
0–5% O2, bal N2) constitutes approximately 37–57 million tons This is the feed ratio obtained from DRM with simultaneous
of CH4 which amounted to 13–20% of total US CH4 production occurrence of the reverse WGS reaction and can be a direct feed
in 2006.5,6 Since CH4 is the primary component of natural for FT synthesis for more selective synthesis of higher hydro-
gas obtained from petroleum reserves7 and landfill gas,5,6 the carbons. For example, Fujimoto et al.,31 used a two-reactor
conversion of CH4 to higher value products will become system with DRM is used to produce syngas which is followed
increasingly important for the foreseeable future. Among the by FT in the second reactor, producing higher alkanes from
most widely studied technologies for conversion of CH4 to DRM-derived syngas.
syngas (mixture of H2 and CO) are various reforming techni-
ques like steam (H2O) reforming (SR), dry (CO2) reforming of 1.2. Brief historical context of CH4 and hydrocarbon
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
2. Reaction thermodynamics
DRM (eqn (4)) is an extremely endothermic reaction:
CH4 + 1/2O2 # CO + 2H2 (DH298K = 36 kJ mol1) (5) Fig. 1 Thermodynamic analysis of total pressures, temperatures and
CO2/CH4 feed ratios below which carbon formation is favored. (Reprinted
CH4 + 2O2 # CO2 + 2H2O 1
(DH298K = 803 kJ mol ) with permission from ref. 38. Copyright 1996 American Chemical Society.)
(6)
The CO2 and H2O produced in eqn (6) act as co-reactants proceeds in the forward direction above 640 1C. Similarly, RWGS
to further carry out SR and DR of CH4.39–41 To avoid high can occur only up to 820 1C and carbon formation can occur due
temperature gradients, Tomishige propose to use fluidized bed to MD above 557 1C and due to BR below 700 1C. Thus they
reactors which would improve heat transfer and stability of the suggested that carbon formation can occur due to both MD and
catalyst. A combination of combustion and reforming would BR in 557–700 1C range. This is in agreement with the result in
make the overall process thermo-neutral and help in limiting Fig. 1, which suggests that at CO2/CH4 ratio of 1, there will be
carbon formation.4 Since the metallic state of Pt is much more carbon formation below 870 1C at 1 atm of total pressure.
stable than that of Ni, for reaction with O2 and CO2 as oxidants, The thermodynamic equilibrium plots for DRM as a func-
noble metals like Pt are preferred. Using membrane reactors tion of temperature at 1 atm are shown in Fig. 2. Fig. 2(a) shows
can also prove beneficial to overcome the thermodynamic the DRM equilibrium amount when only H2, CO, and H2O are
limitations of the reaction; e.g., Pd–Ag membranes have been allowed to form. This calculation shows that the H2/CO ratio at
shown to catalyze DRM and can remove hydrogen selectively all temperatures after 300 1C is between 0.8–1. Formation of
from the product, driving the reaction toward hydrogen and CO H2O by RWGS is only significant between 400–800 1C, which is
formation.42,43 in agreement with the free energy calculations by Wang et al.38
Eqn (4) shows that DRM produces a syngas with a H2/CO However, this same calculation, when a separate solid phase
ratio close to 1 : 1, but the simultaneous occurrence of reverse of carbon is allowed [Fig. 2(b)] to accommodate for MD and BR,
water gas shift (RWGS) (eqn (7)) reaction causes a decrease in shows an entirely different equilibrium composition. The H2/CO
the H2/CO ratio to values o1.18,44 ratio is far greater throughout the temperature range when C(s)
CO2 + H2 # CO + H2O (DH298K = 41.2 kJ mol1) is allowed. The H2/CO ratio at temperatures below 900 1C is
greater than unity because increased carbon formation lowers
DG1 = 8545 + 7.84T (7) the amount of CO formed and hence increases the H2/CO ratio.
Apart from RWGS, other side reactions may occur simulta- Above B900 1C, little carbon is present, bringing the H2/CO
neously with DRM depending on the operating temperature ratio close to 1 : 1. These calculations also show that C(s) forma-
and reactant partial pressure. These include CH4 decomposi- tion is thermodynamically inevitable under 900 1C, in agree-
tion (eqn (8), MD), where CH4 dissociates completely to form ment with Fig. 1.
solid carbon on the catalyst surface and produce H2, and the Nematollahi et al.,45 conducted the same thermodynamic
Boudouard reaction (eqn (9), BR) where CO disproportionates simulations at various pressures and determined that the conver-
to form surface carbon and CO2. sion of CH4/CO2 and the H2/CO yields both drop significantly with
increasing operating pressure. Thus, it is essential to operate at
CH4 # C(s) + 2H2 (DH298K = +75 kJ mol1) low pressures to attain high conversions and high H2/CO yields.
DG1 = 2190 26.45T (8)
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
precursors of the perovskites or pyrochlores. These precursors lower temperatures and limiting the occurrence of simultaneous
are then calcined at 800–1000 1C to oxidize all the carbon and (RWGS and BR) reactions.87 In addition, an ultrapure hydrogen rich
form the highly crystalline ABO3 or A2B2O7 phase.107–109 Gurav stream can be obtained by using the Pd–Ag membrane which has
et al.,106 studied B-site substitution of Ru in SrTiO3 perovskites high permeability and selectivity for H2.123 A brief account of Pd and
and observed that the activity of the catalyst towards DRM does Pd–Ag composite membrane synthesis and its activity towards DRM
not increase in direct proportion to Ru content. From the three is reported by Bosko et al.124 They found that Pd membranes
levels of Ru substitution i.e., 7.9, 15.6, and 31 wt%, the 15.6% showed lower light off temperature and higher conversions com-
catalyst showed higher conversion than the other two catalysts. pared to composite Pd–Ag membrane and that the activity of the Pd
There appears to be an optimum level of metal substitution to membrane is similar to that of Rh/La2O3 powder catalyst. The
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
attain highest activity,106 below the optimum level Ru is well membrane showed stability for about 570 h at 500 1C, which is
dispersed on both the surface of the catalyst and in the bulk. much longer than any supported catalyst at that temperature.
Beyond this optimum level the excess of Ru starts to sinter to A summary of some important DRM results obtained over
form larger clusters or separate out as a different phase. In both different noble metal catalysts is shown in Table 1.
pyrochlores and perovskites, the majority of the active metal is
substituted within the bulk of the crystal structure and only a
small proportion of this active metal is at the surface. 4. Activation mechanism of CH4
De Arauj et al.,18 compared perovskites for DRM with the
B-site composed of Ru and Ni. They observed that the activity and The most kinetically significant and important step in DRM in
carbon formation decreased with the substitution of Ru in the the absence of transport limitations is the adsorption or
perovskite structure. Similar technique was used by Pietraszek activation of CH4. This requires metals like Rh, Pt, Ni on which
et al.,118 where they impregnated Ni on Rh and Ru substituted methane dissociates directly to form carbon, CHx or formyl
Ce0.6Zr0.4O2 (designated: CeZrRh or CeZrRu) fluorite structures. intermediates. Bitter et al.,16 observed that for Pt/ZrO2, after
They observed that substitution of Rh/Ru in the fluorite structure certain amount of metal loading there was no increase in the
increased the activity towards DRM and enhance its resistance to DRM rate with increasing metal content. This suggests that
deactivation. Thus crystalline oxides with ordered crystal lattice CH4 activation occurs at the Pt–ZrO2 interfacial sites and not Pt
are structurally stable catalysts that can withstand high DRM alone. DRM is typically first order in CH472,132,133 and thus an
temperature. With the right proportion of the active metal, active catalyst should have a low activation energy for CH4
these structures also avoid sintering at these high temperatures dissociation to CHx species. Dissociation of CH4 is thermo-
(800–1000 1C) unlike conventional supported catalysts. dynamically most favorable over Rh compared to other transi-
tion metals and is observed to dissociate CH4 starting as low as
3.4. Mesoporous catalysts and membrane reactors for DRM 150 1C.134 The process of activation of CH4 is structure sensitive
Unconventional support materials like silicate structured meso- on supported Rh, Ru, and Pt clusters,20,86,135,136 with a direct
porous catalysts with ordered pore structures have opened new correlation between Rh dispersion and TOF of the catalyst, in
pathways of catalyst design.119 These materials are synthesized by agreement with Wei and Yamaguchi et al.,135,136 who also
hydrothermal synthesis using a surfactant solution as a solvent for demonstrated that the rate of DRM over Rh/Al2O3 is first order
mixing sodium silicate and performing hydrothermal synthesis.119 in CH4 and is independent of CO2 concentration i.e., rCH4 =
These silicate mesoporous structures have very uniform parallel kPCH4.132,133 However, Erdohelyi et al.,134 observed that the rate
pores (minimum tortuosity and hence minimum mass transfer of CH4 dissociation, CO and H2 formation has finite positive
resistance). The pore dimensions of these materials can be altered order dependence on both CH4 and CO2 over Rh/SiO2, Rh/TiO2,
simply by changing the length of the surfactant during the Rh/MgO suggesting significant importance of CO2 activation in
synthesis. Active metals can be then incorporated in the silicate the kinetics of DRM. Munera et al.,71 reported that the rate of
structure by adding the metal precursor solution to the surfactant DRM could have zero order dependence in CO2 on supports like
solution before carrying out hydrothermal synthesis. Such meso- Al2O3 as reported by Wei et al., but with La2O3 as a support the
porous, protonic large pore BEA and FAU type zeolites have been dependence of CO2 is observed to be 0.34 in order. Isotopic
studied for DRM and it is reported that these silica–aluminate studies performed on Rh/Al2O3 by Wang et al.,137 showed that
structures have high thermal stability that is in direct correlation the conversion of CH4 was greater than the conversion of CD4
with the Si/Al ratio of the catalyst.120 Steam dealumination of these suggesting that the dissociation of the C–H bond is the rate-
catalysts can help in increasing the pore volume and the Si/Al ratio determining step in the reforming reaction. Schuurman et al.138
(hence the thermal stability), which increases the contact time of studied the H/D isotope effect for CH4/CD4 pulsing experiment
the reactants with the active metals like Pt and Ni120 resulting in over Ni/SiO2 and Ru/SiO2 and measured the ratio of CH4 con-
higher conversion and lower carbon deposition. verted to isotopically scrambled methane (CH3D, CH2D2, CHD3)
Apart from powdered catalysts (used in fixed bed reactors), to the amount of CH4 converted to CO. That ratio was about 0.1,
membranes with Pd, Ru, Ag have also been used to study DRM suggesting that a significant amount of CH4 is converted to CO
reaction.42,43,121,122 Membranes allow permeation of products and that CH4 dissociates irreversibly to form CO.
away from the catalyst bed which drives the reaction towards There are two mechanisms for dissociation of CH4 on a metal
formation of CO and H2,123 leading to higher conversions at surface as studied by quantum models and by experiments; (1) by
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
Table 1 Summary of key results for noble metal catalysts used for DRM
Pt/ZrO2, Pt/Al2O3, Pt/TiO2 ZrO2 helps in activation of CO2 and promotes activity of DRM. 125
Rh–Ni/BN, Rh–Ni/g-Al2O3 BN showed lower carbon formation as compared to g-Al2O3 and attribute this to Rh–Ni 88
cluster formation on BN which was not possible on Al2O3 due to strong metal support
interaction.
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
Rh–Ni/MgAlO Mg–Al hydrotalcites are very good reforming catalysts as they resist carbon formation by 62
their basic properties, high surface area and thermal stability.
Pt/CexZr1xO2 When Ce/Zr = 1, the catalyst has highest CO2 activation. Promoters like Pr, increases the 126
thermal stability of the catalyst.
Pt/ZrO2 and Pt/Al2O3 After 10 min of exposure to CH4/He; the reactivity of coke towards TPH was greater for 127
Pt/Al2O3 than Pt/ZrO2.
But after the same treatment in CH4/He, when the catalysts were oxidized in CO2, the
reactivity of ZrO2 was greater than Al2O3.
This is attributed to more efficient activation of CO2 by ZrO2 (due to the presence of O
defects) than by Al2O3.
Pd and Pd–Ag composite membranes The activity of the Pd membrane was greater than the Pd–Ag composite membrane. 124
The CH4 conversion for Pd membrane was greater than that at equilibrium at 500 1C.
The carbon balance was about 98% which suggests no carbon deposition.
0.5%Pt/Al2O3, 10%Ni/Al2O3, The monometallic Pt catalyst had lower activity than Ni catalyst but this could be due to 89
0.5%Pt–10%Ni/Al2O3 lower metal content.
However, the bimetallic catalyst showed better activity than either monometallics and
gave stable conversion for over 6500 min without significant deactivation.
0.4%Pt/Al2O3 (N), 0.4%Pt/Al2O3 (C), The catalysts prepared using nanofibrous Al2O3 (N) showed a higher surface area and 128
0.4%Pt–4%Ni/Al2O3 (N) improved metal dispersion as compared to commercial Al2O3 (C).
Promotion of Pt added to the stability of the Ni catalyst against carbon deposition.
1%Pt–1%Ce/ZrO2 This catalysts was prepared by two methods, (a) co-impregnation, and (b) sequential 100
impregnation.
It was reported that the co-impregnated catalyst had higher stability and activity
compared to the sequentially impregnated catalysts.
This higher activity was attributed to the increased Pt–Ce interaction which is a result of
simultaneous heat treatment (calcination) of Pt and Ce precursors as compared to
sequential heat treatment.
1%Pt/ZrO2/SiO2 Varying ratios of ZrO2 : SiO2 were tested and the observed activity and stability for 16 h 90
were in the order 4 : 1 > pure ZrO2 > 3 : 1 > 2 : 1.
(0.3%Pt–10%Ni)/Al2O3; Addition of Pt increased the activity of the catalyst compared to Ni/Al2O3. 129, 130
(0.2%Pt–15%Ni)/Al2O3 Highest activity was observed when the Pt/Ni ratio was the lowest.
Also higher dispersion and least carbon deposition was observed for lowest Pt/Ni ratio.
Co/TiO2, Pt–Co/TiO2, Ru–Co/TiO2 Addition of Pt and Ru improved the dispersion and reducibility of Co. 63
During the reaction metallic form of Co was maintained for the Pt and Ru promoted
catalyst which improved the stability and activity.
0.3%Pt/Al2O3, 0.3% and 1%Na–Al2O3, The order of activity and stability was Na–Al2O3 > K–Al2O3 > ZrO2 > Al2O3. 50
0.3% and 0.5%K–Al2O3, and ZrO2 The presence of Na and K adds to the basicity of the catalyst which helps in activation of
CO2 to form O species which oxidizes carbon to CO, thus increasing resistance to
deactivation.
Low concentration (0.3%) of Na and K showed better stability than higher
concentrations.
Pt/ZrO2, Pt/Ce–ZrO2, Pt/Ce–La–ZrO2 Pt/La–ZrO2 had the highest activity, surface area, and CO2 adsorption capacity. 65
Addition of promoters inhibits particle growth during reaction at 800 1C.
This also increases the metal–support interfacial area which helps in gasification of the
carbon formed during reaction.
2%Ru/TiO2, 2%Ru/SiO2, At 0.1 MPa operating pressure, the Ru/MgO resulted in highest activity and least carbon 131
2%Ru/Al2O3, 2%Ru/MgO formation due to high basicity which facilitates carbonate formation.
At 2 MPa, all catalysts showed almost the same activity and was close to equilibrium
values which suggests the possibility of mass transfer effects and reverse reaction.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
of CH4 to form CHxO species, suggesting that the active site for
DRM over TiO2 supported catalysts is the metal–support inter-
face. Due to the formation of this metal–support interfacial site,
CO or H2 chemisorption could not be used to precisely deter-
mine the dispersion of the metal on the TiO2 as the H/metal
ratio was no longer known. A similar problem in determining
the metal dispersion due to metal–support interaction were
reported by other researchers.149–152
The FTIR spectra during reaction of CH4 with TiO2 sup-
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
improves the syngas yield. The final H2/CO ratio and the extent
of carbon formation depend on the mechanism by which the
methane activates and the ability of the support to activate CO2.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
mask the active metal, thus lowering the activity and too less which could have affected the O exchange ability of Ce, thereby
of an amount would not show any acceptable or significant affecting its activity.
promotion effect on resisting carbon formation. A very effective way of resisting carbon formation is incor-
The addition of CeO2 creates a metal–ceria interaction and poration of the active metal in the support structure with high
helps to create an oxygen reservoir through the redox behavior oxygen mobility.185 This concept has been reported by Pakhare
Ce4+/Ce3+ under reducing conditions.85 This oxygen storage et al.,46,113 and Haynes et al.107–109 where they reported Ru and
capacity and ability to undergo cycles of oxidation–reduction Pt substituted pyrochlores, which have reactive lattice oxygen
by CeO2 provides the metal with oxygen during DRM reaction to that can gasify surface carbon, limiting deactivation due to
suppress carbon deposition.194 Thus CeO2 can be used as a carbon formation. Stagg et al.,65 performed O2 TPD for LaCoO3
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
promoter or as a support itself. The oxygen conductivity of ceria perovskites and observed significant amount of O2 desorbed at
can be increased by doping it with other rare earth metals like 700 1C and proposed that this reactive O2 helps in oxidation of
La, Gd, and Pr.195 Since carbon formation is the major pro- the surface carbon during reforming reaction on Pt/LaCoO3.
blems associated with DRM; increasing the oxygen conductivity Using oxygen-conducting membrane catalysts like La2NiO4 doped
of the catalyst helps in oxidation of the carbon which results in with Pt also increases the gasification of the surface carbon
higher reactant conversion. Sadykov et al.,195 observed that formed during DRM. The surface Pt helps to maintain the DRM
Pr doped 1.4%Pt/Pr0.3–Ce–Zr–O catalyst improved the oxygen activity.198
conductivity of Ce support and thus showed higher CH4 Although some supports are catalytically inert, they may still
conversion as compared to Gd and La doped supports above promote the activity of the catalyst by improving the dispersion
700 1C [Fig. 16]. Similarly, an example is reported by Sazonova of the metal. This phenomenon was observed by Pedrero
et al.,196 who studied Pt promoted fluorite-like oxides (PrCeZrO, et al.,199 who studied Rh supported on TiO2-anatase (TiO2-A)
GdCeZrO, and LaCeZrO), and observed that the Pr-promoted and TiO2-rutile (TiO2-R). The activity of Rh/TiO2-A was much
catalyst had the highest activity above 700 1C followed by higher and more stable than that of Rh/TiO2-R. They attributed
Gd and La-promoted catalyst. The enhanced activity of the this to the promotional effect of the anatase phase on disper-
Pr-catalyst was attributed to the improved oxygen conductivity sion of Rh compared to rutile. Also the increased reducibility of
above 700 1C.196 Rh in Rh/TiO2-A inhibits the oxidation of these Rh atoms
A combination of CeO2 and ZrO2 also performs similar during reaction and keeps the Rh in a metallic state, which is
function of enhancing CO2 activation and improving resistance the active site for CH4 activation.199
of the catalyst towards carbon formation.178 Although it is Another example of the effect of the support on carbon
widely reported in the literature that addition of CeO2 also formation is a study comparing Rh–Ni/BN and Rh–Ni/g-Al2O3.
increases the activity of the catalyst, this is not a completely In this study, Rh–Ni/BN showed less carbon formation than
general conclusion. For example, Damyanova et al.,197 observed Rh–Ni/g-Al2O3, suggesting that the support has an important role
that increasing the CeO2 content of the Pt/ZrO2 catalyst, to play in the oxidation of the carbon formed. Similar to Rh; using
actually decreased the conversion. This contradiction to the other noble metals like Pt48 and Au178 can also be used to promote
generally accepted effect of ceria promotion could be attributed Ni catalysts to increase the stability and improve Ni dispersion and
to the different precursor (diammonium hexanitrato cerate) used thus its DRM activity. However, simply promoting the Ni catalyst
by Damyanova, unlike cerium nitrate used by other researchers with noble metals does not increase the activity unless the appro-
priate synthesis method is adopted. Arbag et al.,119 synthesized
Ni-substituted silicate mesoporous MCM-41 catalysts and pro-
moted it with Rh by using impregnation and hydrothermal syn-
thesis. They observed that although the same amount of Rh was
used to promote the catalyst, the catalyst which had impreg-
nated Rh showed deactivation after 11 h of DRM at 600 1C.
However, the hydrothermally synthesized Rh promoted catalyst
had enhanced activity and time-on-stream stability. Also the
hydrothermally synthesized Rh bimetallic catalysts showed
lower selectivity for RWGS as compared to impregnated
bimetallic catalysts. Thus it is not only the promotion of the
noble metal but also the synthesis method that affects the
stability of the catalyst.
The calcination step is also important. Keeping the synthesis
procedure consistent but changing the gas used to calcine the
catalyst and the calcination temperature also has a significant
effect on the final catalyst performance.175 Steinhauer et al.,60
Fig. 16 Conversion of CH4 at varying temperatures (1 atm) for Pr, Gd, and
studied bimetallic 4%Ni–1%Pd supported on 93%ZrO2–7%La2O3
La promoted Pt/Ln0.3–Ce–Zr–O catalysts. (Reprinted with permission calcined at 200, 400, 600 and 800 1C and observed that the
from ref. 195. Copyright 2010 Elsevier.) catalyst calcined at 600 1C showed the highest activity [Fig. 17].
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
Fig. 17 Comparison of the reactant conversion and syngas yield at 500, 600, 700 1C for 7.5%(Ni0.8Pd0.2) supported on [93%ZrO27%La2O3] as a function
of calcination temperatures of 200, 400, 600, and 800 1C. (Reprinted with permission from ref. 60. Copyright 2009 Elsevier.)
The catalyst calcined at lower temperature resulted in insufficient 7. Kinetics and mechanism of DRM
interaction between Ni and Pd, while, high temperature calci- 7.1. Activation energies of CH4 and CO2
nation resulted in sintering of metal particles. This is attributed
to the influence of the calcination process on increasing the A wide spectrum of catalysts have been studied for DRM, thus a
Ni–Pd interaction-the closer/stronger the interaction, the higher wide range of mechanistic steps have been reported in the litera-
the activity of the catalyst. ture, depending upon the temperature and partial pressure range
Apart from changing the catalyst to control deactivation, used. The sites for activation of CH4 and CO2 depend strongly on
incorporation of additional oxidants like H2O or O2 in the the type of the catalyst used. In case of Pt/SiO2, CH4 and CO2 both
reactant stream can improve the resistance of the catalyst to are activated on Pt metal, however, when Pt is dispersed on ZrO2,
deactivation.58,175,200 A thermodynamic calculation performed CO2 is activated on ZrO2 support due to involvement of the oxygen
with O2 in the DRM feed shows a significant reduction in vacancies and not on Pt.125 In situ XANES study of Pt/ZrO2 under
carbon formation with an increase in O2/CH4 ratio.45 Garcia flowing CO2 has shown that during CO2 dissociation to CO and O;
et al.,58 reported that over Rh–Ni/Al2O3 bimetallic catalysts there was no change in the Pt spectra suggesting that the dis-
addition of small amounts of H2O (steam) along with CH4 sociated O is a part of ZrO2 and not Pt.16 An opposite mechanism
and CO2 improves the gasification of the carbon formed during was observed for Rh/SiO2 where the dissociation of CO2 occurred at
DRM as compared to the gasification carried out by only CO2. Rh site and the metallic Rh was oxidized to Rh+3 as seen in
A similar concept using multiple oxidants was reported by XANES.146 Similar dissociative adsorption of CO2 was proposed
Nematollahi et al.,201 and Soria et al.,200 where they observed by the results obtained from SSITKA study over Ru/SiO2.138
that increasing the concentration of steam as a co-feed inhibits In the presence of La2O3, CO2 is activated on La2O3 forming
the RWGS and increases H2 selectivity while decreasing the CO2 La–oxycarbonates which then react with the carbon formed
conversion. They studied combination of DRM and partial from CH4 activation at the metal–La interface.203
oxidation of CH4 (POM) and observed several advantages of Studying the mechanism of DRM and determining the kinetic
this process; namely, coupling of exothermic (POM) and parameters is important for developing an effective catalyst and
endothermic (DRM) reaction minimizes heat transfer require- for commercializing methane reforming technology. The mecha-
ments. By altering the feed composition of O2 and CO2, the nism and the kinetics of DRM depend on the type of the catalyst
final desired H2/CO ratio between 0.5–2 can be obtained.201 used as well as the reactants involved. A few activation energies
A similar process was reported by McGuire et al.,202 who based on the consumption of CH4 (Ea) and CO2 (Ea) have been
showed that addition of low levels of O2 in the feed significantly reported and selected results are summarized in Table 2.
increases CH4 conversion and decreases carbon formation. The In all cases, the activation energy for CH4 is greater than that
effect of the addition of O2 and H2O is reversible, i.e., the H2/CO based on CO2. This is consistent with other reactions involving
product ratio change when the additional co-reactants are CH4 and is due to the energy required to activate the relatively
added but the normal DRM yields are restored when H2O and stable CH4 molecule.127 For Pt catalysts, the activation energy
O2 are removed from the feed.41,176 This could be perhaps for the rate of CH4 and CO2 disappearance vary for different
because the addition of H2O or O2 brings about a change in the supports. The difference in the activation barrier can be attri-
oxidation state of the metal or changes the kinetics of the buted to the difference in the basicity of the support.
intermediate reaction steps which results in the apparent
change in the DRM yields, but when flow of H2O and O2 are 7.2. Intermediate mechanistic steps of DRM
stopped the oxidation state of the metal reach the metallic state Dissociation of CH4 is typically the most kinetically significant step
which restores the DRM activity of the catalyst.139 in DRM.72,132,133,206 However, Efstathiou et al.,207 conducted SSITKA
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Table 2 Activation energies for DRM over different catalysts pressure in the temperature range 823–1023 K and observed
that the rate-determining step (rds) changed with temperature.
Activation energy
Ea (kcal mol1) They reported that CH4 dissociation was the rds for 823–848 K
Temperature
Catalyst used range (K) CH4 CO2 Ref.
range, whereas the reaction between CHx and CO2 was the rds
in 923–1023 K range. Bradford et al.,68,143,148 have shown in
1%Pt/Al2O3 733–823 21.8 20.2 204
1%Pt/ZrO2 733–823 18.4 15
their detailed study on mechanism of DRM over Pt, Ni and Ru
1%Rh/MgO 773 23.2 20.3 134 catalysts that CH4 dissociates reversibly to form CHx species.
1%Rh/Al2O3 773 18.2 16.2 The dissociative adsorption of CO2 forms CO and O on the
0.5%Rh/Al2O3 600–1100 20 — 92
0.5%Rh/SiO2 15 —
surface, this O reacts with CHx and leads to formation of CHxO.
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
Fig. 18 (A) FTIR spectra for C–H stretching of adsorbed CH3/CH3O species on Rh/SiO2, (B) changes in the ratio of integrated absorbance of CH3 adsorbed
species at 2922 cm1 due to evacuation and presence of 1 Torr of CO2 at 423 K. (Reprinted with permission from ref. 209. Copyright 1997 Springer.)
interfacial region which catalyzes the dissociation and reaction promotion with Pt increases the stability of Ni catalysts. The
of intermediates formed from CH4 and CO2 activation.96 presence of Pt also decreases the inhibition effect of CO on the
Most catalysts studied for DRM, except for the ones with rate of DRM.129,130
inert supports, follow bi-functional pathway for DRM. In this However, a power law model is generally valid for only a
pathway, the activation of CH4 and CO2 occur at two different narrow range of partial pressures. In order to attain a rate model
sites and the reaction between the intermediates takes place at that is valid over a wider range of conditions, a model based on a
the metal–support interface. This bi-functional pathway has fundamentally sound mechanism is needed. Quiroga et al.212
general support in the literature, with the reaction taking place performed kinetic rate modeling on Ni–Rh/Al2O3 catalyst and
on catalysts with active metal, and support having either present a series of mechanistic steps involved in DRM [Fig. 19].
electrophilic or nucleophilic character. For active metals on They then assumed different surface reactions as the rate limiting
inert supports, the metal catalyzes all the surface reactions steps. Using Langmuir–Hinshelwood–Hougen–Watson (LHHW)
and is more prone to deactivation due to carbon deposition or mechanism, they derived a set of 27 rate expressions and fit the
sintering. obtained kinetic data to the rate expressions. They performed the
parameter estimation by minimizing the objective function;
7.3. Kinetic rate modeling
X
n 2
Many researchers have used simple power law models to study F¼ xCH4 ;exp xCH4 ;calc
the reaction mechanism for DRM.9,210,211 These models can be I¼1
used to explain how presence of Pt helps in reducing carbon
formation on the Ni/Al2O3 catalyst. When the Ni/Pt ratio was where, n is the number of conditions the experiments are
75/1, the order in CO2 was 1.4 and when it was 33/1, the order carried out, xCH4,exp is the experimental conversion of CH4
was 0.87. This suggests that the presence of Pt enhances the and xCH4,calc is the conversion of CH4 calculated by the kinetic
reactivity of the oxygen from CO2 and aids in the reaction of rate expression. Minimizing this parameter (F) by using the
this oxygen with the deposited carbon.129,130 This explains why Marquardt’s algorithm gives the best fit values for the adsorption
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
Fig. 19 Kinetic scheme of the DRM mechanism. (Reprinted with permission from ref. 212. Copyright 2007 American Chemical Society.)
and rate constants that are used in the rate expressions. This not suitable for representing the kinetics of the reaction over
methodology of deriving a mathematical model and fitting it with Ir/Al2O3. Based on their experiments they proposed a model
a kinetically relevant dataset makes the model quantitative and [Table 3 and eqn (12)] with CH4 dissociation to surface carbon
predictive which helps in understanding the DRM mechanism. and H as the rate determining step while the oxidation of CHx
Other detailed mechanisms and models have also been pro- to CO, and dissociation of CO2 to CO as fast step.
posed in the literature and statistically compared to experimental Many investigators assume that the activation of CO2 and
results.9,49,53,70,134,143,207,210,213,214 For example, Richardson CH4 takes place on different sites.16,18,216 For instance, Gallego
et al.,210 derived a rate expression based on the LHHW mechanism et al.,206 observed S1 and S2 as sites for activation of CH4 and
where CH4 and CO2 are both adsorbed and these adsorbed CH4 CO2, respectively. They derived a rate model where CH4 disso-
and CO2 take part in the rate determining step. They observed that ciates on S1 to form adsorbed carbon C-S1, and CO2 adsorbs on
the kinetic experimental data obtained over Rh/Al2O3 was in S2 to form CO2-S2. They reported two rate determining steps,
agreement with the derived rate model [eqn (11)]. However, (i) dissociation of CH4, and (ii) oxidation of C-S1 by CO2-S2, which
they did not show the forms of adsorption or the sequence of results in the rate model given by eqn (13). Souza et al.,204
reaction steps that led to this model equation. Luo et al.,49 observed similar bi-functional mechanism with dissociation of
assumed that the dissociation of CHxO species to CO and xH as CH4, and reaction between adsorbed CHx and non-dissociated
the rate determining step but did not present the derived rate adsorbed CO2 as the rds for their rate model [eqn (14)] over
model for the same. Mark et al.,70,215 argued that the conven- Pt/ZrO2. Quiroga et al.,212 proposed twenty-seven different
tional Langmuir–Hinshelwood (LH) or Eley–Rideal models are models varying in sequence of reaction steps like dissociative
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
and associative adsorption of CH4 and CO2. They observed that Acknowledgements
the model that was the best fit to the kinetic data was denoted
by eqn (15) [Table 3] for Ni–Rh/Al2O3 catalyst. The model This material is based upon work supported as part of the
considers dissociative adsorption of CH4 and molecular adsorp- Center for Atomic Level Catalyst Design, an Energy Frontier
tion of CO2. The rate determining step is the reaction between Research Center funded by the U.S. Department of Energy,
surface carbon and adsorbed CO2. Although the types of Office of Science, Office of Basic Energy Sciences under Award
catalyst used (noble or non-noble metal like eqn (13)), tempera- Number DE-SC0001058.
ture and partial pressure range used to study the mechanism
vary [Table 3], the predicted rate determining step remains the References
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
22 J. H. Edwards, Catal. Today, 1995, 23, 59–66. 50 A. D. Ballarini, S. R. de Miguel, E. L. Jablonski, O. A. Scelza
23 S. Yokota, K. Okumura and M. Niwa, Appl. Catal., A, 2006, and A. A. Castro, Catal. Today, 2005, 107–108, 481–486.
310, 122–126. 51 A. K. Avetisov, J. R. Rostrup-Nielsen, V. L. Kuchaev,
24 O. R. Inderwildi, S. J. Jenkins and D. A. King, Angew. Chem., J. H. B. Hansen, A. G. Zyskin and E. N. Shapatina, J. Mol.
Int. Ed., 2008, 47, 5253–5255. Catal. A: Chem., 2010, 315, 155–162.
25 L. Kapokova, S. Pavlova, R. Bunina, G. Alikina, T. Krieger, 52 C. Carrara, J. Munera, E. A. Lombardo and L. M. Cornaglia,
A. Ishchenko, V. Rogov and V. Sadykov, Catal. Today, 2011, Top. Catal., 2008, 51, 98–106.
164, 227–233. 53 P. Ferreira-Aparicio, C. Marquez-Alvarez, I. Rodriguez-
26 Z. L. Zhang, V. A. Tsipouriari, A. M. Efstathiou and Ramos, Y. Schuurman, A. Guerrero-Ruiz and C. Mirodatos,
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
76 C. E. Daza, J. Gallego, J. A. Moreno, F. Mondragon, 102 A. Ballarini, F. Basile, P. Benito, I. Bersani, G. Fornasari,
S. Moreno and R. Molina, Catal. Today, 2008, 133, 357–366. S. de Miguel, S. C. P. Maina, J. Vilella, A. Vaccari and
77 M. I. Dimitrijewits, M. M. Guraya, C. P. Arciprete, O. A. Scelza, Appl. Catal., A, 2012, 433, 1–11.
A. C. Luna and A. Becerra, Granular Matter, 2001, 3, 103 T. H. Gardner, J. J. Spivey, A. Campos, J. C. Hissam, E. L.
101–104. Kugler and A. D. Roy, Catal. Today, 2010, 157, 166–169.
78 C. A. M. Abreu, D. A. Santos, J. A. Pacifico and N. M. Lima 104 T. H. Gardner, J. J. Spivey, E. L. Kugler, A. Campos, J. C.
Filho, Ind. Eng. Chem. Res., 2008, 47, 4617–4622. Hissam and A. D. Roy, J. Phys. Chem. C, 2010, 114, 7888–7894.
79 Y. J. O. Asencios and E. M. Assaf, Fuel Process. Technol., 105 T. H. Gardner, J. J. Spivey, E. L. Kugler and D. Pakhare,
2013, 106, 247–252. Appl. Catal., A, 2013, 455, 129–136.
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
80 Z. Y. Hou, O. Yokota, T. Tanaka and T. Yashima, Appl. 106 H. R. Gurav, R. Bobade, V. L. Das and S. Chilukuri, Indian
Catal., A, 2003, 253, 381–387. J. Chem., Sect. A: Inorg., Bio-inorg., Phys., Theor. Anal. Chem.,
81 G. Sierra Gallego, F. Mondragon, J. Barrault, J.-M. Tatibouet 2012, 51, 1339–1347.
and C. Batiot-Dupeyrat, Appl. Catal., A, 2006, 311, 164–171. 107 D. J. Haynes, D. A. Berry, D. Shekhawat and J. J. Spivey,
82 Y. H. Hu and E. Ruckenstein, J. Phys. Chem. B, 1997, 101, Catal. Today, 2008, 136, 206–213.
7563–7565. 108 D. J. Haynes, D. A. Berry, D. Shekhawat and J. J. Spivey,
83 J. H. Bitter, K. Seshan and J. A. Lercher, J. Catal., 1998, 176, Catal. Today, 2009, 145, 121–126.
93–101. 109 D. J. Haynes, A. Campos, D. A. Berry, D. Shekhawat, A. Roy
84 P. Ferreira-Aparicio, I. Rodriguez-Ramos, J. A. Anderson and J. J. Spivey, Catal. Today, 2010, 155, 84–91.
and A. Guerrero-Ruiz, Appl. Catal., A, 2000, 202, 183–196. 110 A. T. Ashcroft, A. K. Cheetham, J. S. Foord, M. L. H. Green,
85 P. Djinovic, J. Batista and A. Pintar, Int. J. Hydrogen Energy, C. P. Grey, A. J. Murrell and P. D. F. Vernon, Nature, 1990,
2012, 37, 2699–2707. 344, 319–321.
86 P. Gronchi, C. Mazzocchia and R. Del Rosso, Energy Convers. 111 A. T. Ashcroft, A. K. Cheetham, M. L. H. Green and
Manage., 1995, 36, 605–608. P. D. F. Vernon, Nature, 1991, 352, 225–226.
87 P. Ferreira-Aparicio, A. Guerrero-Ruiz and I. Rodriguez- 112 A. T. Ashcroft, A. K. Cheetham, R. H. Jones, S. Natarajan,
Ramos, Appl. Catal., A, 1998, 170, 177–187. J. M. Thomas, D. Waller and S. M. Clark, J. Phys. Chem.,
88 J. C. S. Wu and H. C. Chou, Chem. Eng. J., 2009, 148, 1993, 97, 3355–3358.
539–545. 113 D. Pakhare, D. Haynes, D. Shekhawat and J. Spivey, Appl.
89 S. R. de Miguel, I. M. J. Vilella, S. P. Maina, D. S. Jose- Petrochem. Res., 2012, 2, 27–35.
Alonso, M. C. Roman-Martinez and M. J. Illan-Gomez, 114 D. Pakhare, H. Wu, S. Narendra, V. Abdelsayed, D. Haynes,
Appl. Catal., A, 2012, 435, 10–18. D. Shekhawat, D. Berry and J. Spivey, Appl. Petrochem. Res.,
90 G. K. Reddy, S. Loridant, A. Takahashi, P. Delichere and 2013, 3, 117–129.
B. M. Reddy, Appl. Catal., A, 2010, 389, 92–100. 115 M. A. Subramanian, G. Aravamudan and G. V. S. Rao, Prog.
91 B. Sarkar, S. Suman, R. Tiwari, R. K. Singha, S. Ghosh, Solid State Chem., 1983, 15, 55–143.
Shankha, S. Acharyya, L. N. S. Konathala, C. Pendem, 116 P. J. Wilde and C. R. A. Catlow, Solid State Ionics, 1998, 112,
K. Mantri and R. Bal, Indian J. Chem., Sect. A: Inorg., Bio- 173–183.
inorg., Phys., Theor. Anal. Chem., 2012, 51, 1348–1353. 117 V. R. Choudhary, K. C. Mondal, A. S. Mamman and
92 J. Nakamura, K. Aikawa, K. Sato and T. Uchijima, Catal. U. A. Joshi, Catal. Lett., 2005, 100, 271–276.
Lett., 1994, 25, 265–270. 118 A. Pietraszek, B. Koubaissy, A. C. Roger and A. Kiennemann,
93 V. A. Tsipouriari, A. M. Efstathiou, Z. L. Zhang and Catal. Today, 2011, 176, 267–271.
X. E. Verykios, Catal. Today, 1994, 21, 579–587. 119 H. Arbag, S. Yasyerli, N. Yasyerli and G. Dogu, Int.
94 S. Yokota, K. Okumura and M. Niwa, Catal. Lett., 2002, 84, J. Hydrogen Energy, 2010, 35, 2296–2304.
131–134. 120 A. N. Pinheiro, A. Valentini, J. M. Sasaki and A. C. Oliveira,
95 H. Y. Wang and E. Ruckenstein, Appl. Catal., A, 2000, 204, Appl. Catal., A, 2009, 355, 156–168.
143–152. 121 F. R. Garcia-Garcia, M. A. Soria, C. Mateos-Pedrero,
96 M. C. J. Bradford and M. A. Vannice, Catal. Lett., 1997, 48, A. Guerrero-Ruiz, I. Rodriguez-Ramos and K. Li, J. Membr.
31–38. Sci., 2013, 435, 218–225.
97 M. Sigl, M. C. J. Bradford, H. Knozinger and M. A. Vannice, 122 B. Faroldi, C. Carrara, E. A. Lombardo and L. M. Cornaglia,
Top. Catal., 1999, 8, 211–222. Appl. Catal., A, 2007, 319, 38–46.
98 A. F. Lucredio and E. M. Assaf, J. Power Sources, 2006, 159, 123 F. Gallucci, S. Tosti and A. Basile, J. Membr. Sci., 2008, 317,
667–672. 96–105.
99 S. M. Stagg, E. Romeo, C. Padro and D. E. Resasco, J. Catal., 124 M. L. Bosko, J. F. Munera, E. A. Lombardo and L. M.
1998, 178, 137–145. Cornaglia, J. Membr. Sci., 2010, 364, 17–26.
100 S. Ozkara-Aydinoglu, E. Ozensoy and A. E. Aksoylu, 125 A. N. J. vanKeulen, K. Seshan, J. Hoebink and J. R. H. Ross,
Int. J. Hydrogen Energy, 2009, 34, 9711–9722. J. Catal., 1997, 166, 306–314.
101 M. Garcia-Dieguez, I. S. Pieta, M. C. Herrera, M. A. Larrubia 126 V. A. Sadykov, E. L. Gubanova, N. N. Sazonova, S. A.
and L. J. Alemany, Appl. Catal., A, 2010, 377, 191–199. Pokrovskaya, N. A. Chumakova, N. V. Mezentseva,
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.
View Article Online
A. S. Bobin, R. V. Gulyaev, A. V. Ishchenko, T. A. Krieger 156 P. Chen, H. B. Zhang, G. D. Lin and K. R. Tsai, Appl. Catal.,
and C. Mirodatos, Catal. Today, 2011, 171, 140–149. A, 1998, 166, 343–350.
127 K. Nagaoka, K. Seshan, J. A. Lercher and K. Aika, Catal. 157 J. Guo, H. Lou, L. Mo and X. Zheng, J. Mol. Catal. A: Chem.,
Lett., 2000, 70, 109–116. 2010, 316, 1–7.
128 M. Garcia-Dieguez, I. S. Pieta, M. C. Herrera, M. A. Larrubia 158 R. P. Turcotte, J. O. Sawyer and L. Eyring, Inorg. Chem,
and L. J. Alemany, J. Catal., 2010, 270, 136–145. 1969, 8, 238–246.
129 S. Ozkara-Aydinoglu and A. E. Aksoylu, Int. J. Hydrogen 159 S. Irusta, L. M. Cornaglia and E. A. Lombardo, Mater.
Energy, 2011, 36, 2950–2959. Chem. Phys., 2004, 86, 440–447.
130 S. Ozkara-Aydinoglu and A. E. Aksoylu, Chem. Eng. J., 2013, 160 A. Olafsen, A. K. Larsson, H. Fjellvag and B. C. Hauback,
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2014
View Article Online
182 L. Guczi, G. Stefler, O. Geszti, I. Sajo, Z. Paszti, A. Tompos 199 C. Mateos-Pedrero, S. R. Gonzalez-Carrazan, M. A. Soria
and Z. Schay, Appl. Catal., A, 2010, 375, 236–246. and P. Ruiz, Catal. Today, 2013, 203, 158–162.
183 J. Barbier, Appl. Catal., 1986, 23, 225–243. 200 M. A. Soria, C. Mateos-Pedrero, A. Guerrero-Ruiz and
184 S. M. Stagg-Williams, F. B. Noronha, G. Fendley and I. Rodriguez-Ramos, Int. J. Hydrogen Energy, 2011, 36,
D. E. Resasco, J. Catal., 2000, 194, 240–249. 15212–15220.
185 B. Koubaissy, A. Pietraszek, A. C. Roger and A. Kiennemann, 201 B. Nematollahi, M. Rezaei and M. Khajenoori, Int.
Catal. Today, 2010, 157, 436–439. J. Hydrogen Energy, 2011, 36, 2969–2978.
186 V. A. Tsipouriari, A. M. Efstathiou and X. E. Verykios, 202 N. E. McGuire, N. P. Sullivan, O. Deutschmann, H. Y. Zhu
J. Catal., 1996, 161, 31–42. and R. J. Kee, Appl. Catal., A, 2011, 394, 257–265.
Published on 07 February 2014. Downloaded by Oregon State University on 22/06/2014 23:47:36.
187 J. M. Rynkowski, T. Paryjczak, M. Lenik, M. Farbotko and 203 X. E. Verykios, Int. J. Hydrogen Energy, 2003, 28, 1045–1063.
J. Goralski, J. Chem. Soc., Faraday Trans., 1995, 91, 3481–3484. 204 M. Souza, D. A. G. Aranda and M. Schmal, J. Catal., 2001,
188 J. Barbier, G. Corro, Y. Zhang, J. P. Bournonville and 204, 498–511.
J. P. Franck, Appl. Catal., 1985, 13, 245–255. 205 A. Topalidis, D. E. Petrakis, A. Ladavos, L. Loukatzikou and
189 K. Tao, Y. Zhang, S. Terao and N. Tsubaki, Catal. Today, P. J. Pomonis, Catal. Today, 2007, 127, 238–245.
2010, 153, 150–155. 206 G. Sierra Gallego, C. Batiot-Dupeyrat, J. Barrault and
190 A. G. Bhavani, W. Y. Kim, J. Y. Kim and J. S. Lee, Appl. F. Mondragon, Ind. Eng. Chem. Res., 2008, 47, 9272–9278.
Catal., A, 2013, 450, 63–72. 207 A. M. Efstathiou, A. Kladi, V. A. Tsipouriari and X. E.
191 F. Meshkani and M. Rezaei, Int. J. Hydrogen Energy, 2010, Verykios, J. Catal., 1996, 158, 64–75.
35, 10295–10301. 208 M. C. J. Bradford and M. A. Vannice, J. Catal., 1998, 173,
192 D. L. Trimm, Catal. Today, 1999, 49, 3–10. 157–171.
193 E. Nikolla, J. Schwank and S. Linic, J. Catal., 2009, 263, 209 J. Rasko and F. Solymosi, Catal. Lett., 1997, 46, 153–157.
220–227. 210 J. T. Richardson and S. A. Paripatyadar, Appl. Catal., 1990,
194 M. Ocsachoque, J. Bengoa, D. Gazzoli and M. G. Gonzalez, 61, 293–309.
Catal. Lett., 2011, 141, 1643–1650. 211 A. Erdohelyi, J. Cserenyi, E. Papp and F. Solymosi, Appl.
195 V. Sadykov, V. Muzykantov, A. Bobin, N. Mezentseva, Catal., A, 1994, 108, 205–219.
G. Alikina, N. Sazonova, E. Sadovskaya, L. Gubanova, 212 M. M. B. Quiroga and A. E. C. Luna, Ind. Eng. Chem. Res.,
A. Lukashevich and C. Mirodatos, Catal. Today, 2010, 2007, 46, 5265–5270.
157, 55–60. 213 J. B. Claridge, A. P. E. York, A. J. Brungs, C. Marquez-
196 N. N. Sazonova, V. A. Sadykov, A. S. Bobin, S. A. Alvarez, J. Sloan, S. C. Tsang and M. L. H. Green, J. Catal.,
Pokrovskaya, E. L. Gubanova and C. Mirodatos, React. 1998, 180, 85–100.
Kinet. Catal. Lett., 2009, 98, 35–41. 214 T. Osaki, T. Horiuchi, K. Suzuki and T. Mori, Catal. Lett.,
197 S. Damyanova, B. Pawelec, K. Arishtirova, M. V. M. Huerta 1995, 35, 39–43.
and J. L. G. Fierro, Appl. Catal., B, 2009, 89, 149–159. 215 M. F. Mark, F. Mark and W. F. Maier, Chem. Eng. Technol.,
198 V. V. Kharton, A. A. Yaremchenko, E. V. Tsipis, A. A. 1997, 20, 361–370.
Valente, M. V. Patrakeev, A. L. Shaula, J. R. Frade and 216 J. J. Guo, H. Lou, H. Zhao, D. F. Chai and X. M. Zheng,
J. Rocha, Appl. Catal., A, 2004, 261, 25–35. Appl. Catal., A, 2004, 273, 75–82.
This journal is © The Royal Society of Chemistry 2014 Chem. Soc. Rev.