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A review of C1 chemistry synthesis using yttrium-stabilized zirconia catalyst

Antonius Indarto, Jae-Wook Choi, Hwaung Lee, Hyung Keun Song
(Plasma-Catalyst Chemical Pmces,s. Koma Institute of Science and Technology Cheonngryung, Seoul. South Korea)
Received 21 May 2007: revised 30 July 2007

Abstract: C1 chemistry based on synthesis gas, methane. and carbon dioxide offers many routes to industrial chemicals. The reactions related
to the synthesis of gas can be classified into direct and indirect approach for making such products, such as acetic acid, dimethyl ether, and
alcohol. Catalytic syngas processing is currently done at high temperatures and pressures, conditions that could be unfavorable for the life of
the catalyst. Another issue of Cl chemistry is related to the methane-initiated process. It has been known that direct methane conversions are
still suffering from low yields and selectivity of products resulting in unprofitable ways to produce products, such as higher hydrocarbons,
methanol, and so on. However. many experts and researchers are still trying to find the best method to overcome these barriers, for example,
by finding the best catalyst to reduce the high-energy banier of the reactions and conduct only selective catalyst-surface reactions. The appli-
cation of Yttria-Stabilized Zirconia (YSZ) and its combination with other metals for catalyzing purposes are increasing. The existence of an
interesting site that acts as oxygen store could be the main reason for it. Moreover, formation of intermediate species on the surface of YSZ
also contributes significantly in increasing the production of some specific products. Understanding the phenomena happening inside could
be necessary. In this article, the use of YSZ for some CI chemistry reactions wa? discussed and reviewed.

Keywords: C1chemistry; methane; synthesis gas; methanol; yttria-stabilized zirconia; catalyst; oxygen storage; rare earths

Recent concern over the availability and cost of petroleum
feedstocks has given rise to a growing interest in later native
carbon sources, such as natural gas, coal, biomass, shale oil,
and tar sands. A potential development is the gasification of
all these resources into synthesis gas and its use as a com-
mon feedstock for the chemical industry. In parallel with the
knowledge of C, chemistry synthesis, the development of
the manufacturing process to bring it to the real industrial
level is needed.
CI chemistry usually occurs on catalytic reactions and
much work was reported in the past decade on these proc-
esses. Some processes have already been well established,
for example, methanol from synthesis gas, but the process
has enough scope for improvement. Direct or indirect syn-
thesis gas (Corn2)processes are still suffering from low
yields and selectivity under low pressure and temperature
condition. It means that the process should be done at condi-
tions higher than atmospheric pressure and ambient tem-
perature. A similar problem is faced for methane conversion
process. Usually, methane is converted by Oxidative Cou-
pling of Methane (OCM), a promising process for direct
conversion of natural gas into Cz hydrocarbons (ethylene
and ethane)"41, synthesis gas[", and methanol products.
Foundation item: Project supported by the Global R&D Program of the Korea Foundation for International Cooperation of Science and Technology (KICOS)
Corresponding author: Antonius Indarto (E-mail: indarto~antonius@yahoo.com;Tel.: +82- 10-2296-3748)
Among many types of OCM, CH, combined with CO1 re-
forming is However, because of deep oxida-
tion reactions in the gas phase and on the catalyst surface,
the Cz yield of OCM achieved so far on any catalyst oper-
ated in conventional packed-bed reactor is less than 25%
when C2 selectivity was higher than 50%. This is far below
the requirement for making OCM economically attractive
(~300/0-40%)'4'.
1 Oxygen-storagecatalyst
Previously, research on C1 chemistry was focused on the
method of activating the reactants on the surface of the
catalyst. As the result was not economically viable, it forced
the researchers to find new ideas to boost the quantity of the
products. Till date, many catalyst studies have increasingly
focused on oxygen-ion oxides18-"'. In partial oxidation reac-
tions in which oxygen plays the key role, the existence of
space lattice storage to control the oxygen surface on the
catalyst surface is necessary. From this point of view, the
oxygen-ion conducting oxide plays a part on the catalytic
reaction because of the oxygen storagdtransport of the s u p
or to the generation of active centers at the interface
2 JOURNAL OF RARE EARTHS, Vol. 26, No. I , Feb. 2008

between metal and ~upport'~.'~~. In general, it is known that
defects on the surface of the material, that is, the catalyst of
the metal oxides, can act as a vacant oxygen site, which is
important in the surface chemistry'l6I.
Lattice oxygen ions are often involved in reactions over
oxide catalysts. Most of the partial oxidation reactions pro-
ceed via a Mars-van Krevelen mechanism, in which lattice
oxygen ions are incorporated into the products[171. The cycle
for catalytic partial oxidation is closed via replenishment of
the extracted lattice oxygen ions through the dissociative
adsorption of molecular oxygen at the surface'18'.
Previous studies indicated that using such materials as
supports could significantly enhance the catalytic activity of
a second metal addition, for example, F'd8', Rh'"', and
CuOL12*141 for CO oxidation and NO reduction. Such maten-
als may also act as catalysts, and might enhance the selectiv-
ity of specific products, for example, CO hydrogenati~n'~.'~~,
andor reactant conversion rate, for example, decomposition
of formic acid[I5].Although the detailed mechanisms are still
confusing in some parts, sometimes ambiguous and rather
controversial, these improvements in catalytic activity have
been attributed to the effects of oxygen ionic trans-
port[8,1 1.12.141 , interfacial metal-support i n t e r a ~ t i o n l ~ 'or
~ ~ ' ~ ~v] a c a n c i e ~ ' ~ ~ ' ~ ~ ~ .
surface oxygen vacancies of these oxygen-ion-conducting
oxides[9910.14.151
Among all transition metal group compounds, yttrium
(oxide) and zirconium (oxide) with its mixing combinations
have attracted many researchers' interest. It suggests that ei-
ther y3+or ZI-~must act as a trapping center for oxygen va-
cancies in yttria-stabilized zirconia (YSZ) at low tempera-
tures. An extended X-ray absorption fine structure ( E M S )
study indicated that an oxygen vacancy was sited adjacent to
Zrb"91. However, analysis of the molecular dynamics
showed that oxygen vacancies were trapped at the sec-
ond-neighbor positions to Y3+[201. Some knowledge about the
trapping center would be obtained if Y3+ or Zr4 ions were
partially replaced by other trivalent or tetravalent ionic spe-
cies, because such replacements would change the bonding
nature between the trapping center and an oxygen vacancy.
over, it has a very low thermal conductivity that allow US to
operate at higher temperatures and prevent the deactivation
of a possible second dopant metal on its surface, for exam-
ple, because of agglomeration.
Yttria doping of Zr02 was used to generate a single phase
(cubic) and to introduce known concent cations of anion
vacancies. The stabilization of the cubic structure is accom-
plished by direct substitution of trivalent yttria cations to the
host lattice Zr4' cation. As the dopant cation is of lower va-
lence than the host cation, oxygen vacancies are created to
preserve lattice neutrality. Spectroscopic studies have shown
that the trivalent Y and tetravalent Zr cations are statistically
distributed[241 and that the Zr cations are nearest neighbors to
the anion vacanciesr191. These vacancies increase the electri-
cal conductivity, with diffusing oxygen ions being the pri-
mary charge ~arrier'~~~"'. This diffusion of oxygen ions has
been associated with lattice vacancy migration'25*261.
The number of oxygen vacancies in ZrO2 can be in-
creased significantly by doping with lower valence metal
ions, such as Y3+and Ca2'. Compared with single ZrO2, the
improved catalytic performance of YSZ in oxidation cataly-
sis has been attributed to a high concentration of oxygen
3 YSZ as a catalyst and its mechanism
Although YSZs have received extensive attention with re-
spect to oxygen sensors, electrochemistry, and fuel cells'30',
the role of YSZ on the chemical synthesis reaction has sel-
dom been addressed. In this section, the authors discuss
briefly about catalytic C1 reactions using YSZ and its pro
posed mechanism.

2 Property YSZ catalyst

The oxides of zirconium form three different phases,
monoclinic, tetragonal, and cubic'2'.221.The monoclinic
phase is stable below 1200 "C. The tetragonal phase is nor-
mally stable above 1200 "C, but can be obtained in a me-
tastable condition at much lower temperatures with the
crystal structure of zirconia particles under 300 angstrom in
diameter[231.The stable cubic phase is only formed at tem-
peratures >2280 "C, but at room temperature, it can occur by
Fig.1 Crystal phase transformation of yttnum addition on z102
the addition of other oxides such as Y203 and CaO. More-
Antvnius Indarto et al., A review of CI chemistry synthesis using yttrium- mbilized zirconia catalyst
3.1 Oxidative methane conversion to synthesis gas
The use of YSZ for the oxidative methane conversion to
synthesis gas was investigated first by Stegh~is[~" and
S t ~ b b e r l ~They
~ ' . used some oxide catalysts, such as Zr02,
Y203,La203/2r02,YSZ, and Ti02 for comparison purposes.
Among these irreducible oxides, YSZ was the most active
catalyst for synthesis gas production. All these catalysts
show lower activity and selectivity compared to metal cata-
lysts but very superior in term of stability. The conversion of
methane was less than 5% at temperature below 800 "C I".
Introduction of second metal-based reforming catalyst was
proposed to increase the activity and selectivity. The second
metal-based reforming catalyst, doped on the YSZ, is stable
as contact reaction with oxygen at high temperatures is
avoided'33'.
-0
means absorbed oxygen on the surface of the catalyst
(YSZ). The above-mentioned mechanism has been investi-
gated further by controlling the input of water to the sys-
ternP4'.Higher concentration of water decreases the forma-
tion rate of formate, that is. the selectivity of CO and H? in-
creases.
3.2 Methanol from synthesis gas
Methanol can be produced from synthesis gas in a cata-
lytic reaction over ZrO2 at atmospheric pressure'3s73"'and
over both ZrOz and YSZ at 35x10' CO and CO/H?
In the high temperature process, the methanol could still
be formed'@'.However, the mechanisms could be different
as the existence of H 2 0 is not sufficient. He et al. proposed
that this methanol is derived from a surface methyl for-
3
On the basis of the relation between methane conversion
and selectivities over ZIQ, Stobbe concluded that CO and
H2 are the primary products of oxidative methane conver-
sion over ZrOz, whereas C02 is formed by water-gas shift
and oxidation of CO'321.Steghuis proposed a reaction
mechanism of methane oxidation over YSZ, including ho-
molitic dissociation of methane over oxygen vacant sites
followed by conversion to CO, HZ, and H20 via the forma-
tion and decomposition of formaldehyde (CH20) as a single
intemiediate spe~ies'~''. C02 is produced by further oxida-
tion reaction of the intermediate. Instead of only formalde-
hyde, the existence of formate (CHOC-) species on the sur-
face of catalyst should also be counted because the H2KO
ratio in the product mixture was significantly larger than one
that was observed, implying that formaldehyde cannot be
the only source of CO and H2l5'.
interaction with YSZ could be the key point of the reaction.
On the surface of the YSZ, the absorbed CO is transformed
into intermediate formate species at an earlier stage137'.It
was supported by the Fourier transform infrared (FTIR)
analysis which showed the existence of assigned formate
bands''8'. Then, the reduction of formate to methoxide
occurs on the surface oxygen anion v a c a n ~ y [ ~and
~ * ~fi-' ~
nally by the reaction between absorbed H20 and metox-
ide to form methanol. The schematic path is illustrated as
follows:
mate-like intermediate. This intermediate was postulated to
form by a nucleophilic attack of CH~0'"1.42'
on f ~ r m y l ' or
~~'
f~rmate'~''.
The simplified mechanisms are as follows:
4 JOURNAL OF RARE EARTHS, Vol. 26, No. 1, Feb. 2008
Real quantitative experiments of methane synthesis using
YSZ was done by Indarto et al.'43"41. It showed that the
methanol produced by addition of YSZ was significantly
higher than other metal oxide catalysts such as A1203 and
Ti02.Moreover, the addition of second metal to the catalyst
improved the selectivity of methanol up to c.a. 20%[#].Un-
fortunately, no investigation on the reaction mechanisms
was done.
3.3 Hydrocarbons from synthesis gas and methane
conversion
Ekerdt et al. found that certain hydrocarbons could be
synthesized over Zr02 and YSZs from CO/H245.461 and
methane oxidation[471.During the past year the research in-
volving yttria-stabilized zirconia (CZA) in the chemical
synthesis process have focused on two issues: confiiation
that anion vacancies are the active slues for CO activation
and hydrogenation, and the influence of additives on the re-
actions that occur during isosynthesis.
In the case of CO hydrogenation reaction, FTIR analysis
proved that oxygen vacancies of the oxides are the active
sites in which formaldehyde and formate were both shown
to be reaction intermediates. The hydrocarbon formation
from syngas is initiated by the reaction between CO (or COz)
with absorbed OH or H. It means that it requires having OH
or H attached on the surface of the catalyst to formate.
Based on the results of in situ FTIR and both steady state
and transient experiments, a reaction scheme was proposed.
-p-\
OH H / more complex catalyst system has been proposed to avoid
co,A&)
For the second case of higher hydrocarbon (ethane and
ethylene) synthesis from methane oxidation, the ratio of
methane to oxygen could be an important point. Liipena-Ray
and Middleton mentioned that at high oxygen flows, mean
low methane to oxygen ratios, the catalyst was not useful as
the gaseous phase reaction is more dominant and reaction
goes to methane oxidation reaction or methane combus-
t i ~ n ' ~By
~ ] measuring
. the polarization of oxygen evolution
or reduction, it was postulated that oxygen transfers are most
likely involved in catalytic partial oxidation of methane. The
C2 selectivity among the products was very high (-86%) at
4% of C2 yield. However, the mechanistic details, particu-
larly the role of oxygen vacancies and that of lattice oxygen
ions in the partial oxidation of methane, are still not clear.
Moreover, the nature of the oxygen species, such as surface
lattice oxygen ions or adsorbed oxygen, in the activation of
methane is still a matter of controversy.
3.4 Methane oxidation using C 0 2
Currently the reaction of methane oxidation using C 02 is
becoming a hot topic and attracts the interest of many people
for environmental and industrial reasons. Both COz and C h
are considered as harmful greenhouse gasesrs7] and this re-
action provides a means of disposing or recycling these
gases. CH4/C02reforming also provides an important route
to produce CO-rich synthesis gas or extremely pure CO for
the synthesis of chemicals such as acetic acid, dimethyl ether,
and alcohols1481.Numerous authors have investigated various
metals, such as: Rh[50,5'1, Pt[521,and Pd[531for CH4/C02
reforming. Most authors preferred Rh catalysts, owing to
their good activity and stability. Meanwhile, Ni catalysts are
commercially more interesting than noble metals but suffer
the disadvantage of a high rate of coke formation. From the
perspective of relative price and good availability, Pt is a
reasonable compromise.
Several have c o n f iie d that Zr02 is a very
effective support for Pt catalysts; such combinations are not
only more active but also more stable than Pt supported on
other materials. Bitter et al.'541showed that only 5% of cata-
lyst deactivation occurred after 50 h of the operation. It was
hypothesized that the oxygen vacancies could be used to ac-
tivate C02 for CO:! reforming of C h at higher temperature
(>600 "C). Some other dopant metals or treatments were
also hied on the YSZ to enhance the better performance of
the original one, but some suffered from the degradation
performance, such as carbon deposition on Ni catalyst. The
last case was also faced when YSZ and Ni were used as the
electrode for the electrochemical process[571.In this case, a
this problem, for example, by the addition of cerium[58'.
Ceria is an effective catalyst for steam reforming and the
oxidation of hydrocarbon^'^^'. The investigation of nickel
catalyst on ceria has been done[571 and appears to be appro-
priate to develop a catalyst that is resistant to carbon deposi-
tion and is also a stable operation for extended periods of
time.
Antonius lndarto et al., A review of C, chemistry synthesis using yttrium-stabilized zirconia catalyst
4 Conclusion
Some remarkable investigations on Y SZ catalyst applica-
tion for CI chemistry were discussed. The formation of for-
mate on the surface of YSZ as the important species in al-
most all CI chemistry reactions was showed. In some cases,
the use of YSZ could boost the performance of the catalyst
by increasing the selectivity and yields of products. The bet-
ter stability of YSZ-supported catalyst was also a point that
should be counted. However, it must be emphasized that
these results in the majority of cases were of mainly aca-
demic interest, but it could create the way to the future ap-
plication of YSZ. As few research deals with YSZ for C,
chemistry, there are still many opportunities for the devel-
opment of the catalyst for other C, chemistry reactions.
Acknowledgment: The first author is thankful to the Korea
Institute of Science and Technology and the Korea Univer-
sity for the study supports.
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