Applied Catalysis A: General 282 (2005) 237–245

www.elsevier.com/locate/apcata

The influence of Pd–Ag catalyst restructuring on the activation energy

for ethylene hydrogenation in ethylene–acetylene mixtures
Hugo Zeaa, Kelvin Lestera, Abhaya K. Datyea,*, Ed Rightorb,
Robert Gulottyb, Wendy Watermanb, Michael Smithc
a
Center for Microengineered Materials and Department of Chemical and Nuclear Engineering,
Farris Engineering Center 203, University of New Mexico, Albuquerque, NM 87131, USA
b
Dow Chemical Company, Midland, MI 48667, USA
c
Dow Chemical Company, Freeport, TX 77541, USA
Received 21 August 2004; received in revised form 2 December 2004; accepted 14 December 2004
Available online 21 January 2005

Abstract

Hydrogenation of acetylene–ethylene mixtures was studied on Pd/SiO2 and Pd–Ag/SiO2 under conditions that correspond to ‘‘front-end’’
hydrogenation of acetylene. The presence of excess H2 under ‘‘front-end’’ hydrogenation conditions can lead to thermal runaway due to the
exothermic reaction of ethylene and H2. In previous work, we found that activation energy was sensitive to catalyst pretreatment: high
temperature treatment in H2 leading to lower apparent activation energy, while pretreatment under oxidizing conditions leading to higher
activation energies for ethylene hydrogenation. Since ethylene hydrogenation is a known structure-insensitive reaction, it was puzzling that
the apparent activation energy should be so sensitive to catalyst pretreatment. As we show in this work, the presence of co-adsorbed CO
(which is present during ‘‘front-end’’ hydrogenation), and changes in the surface structure of Pd–Ag surfaces together modify the apparent
activation energy for ethylene hydrogenation. In situ infrared spectroscopy of adsorbed carbon monoxide reveals how the presence of Ag
modifies the proportion of bridged and linearly bound CO on Pd/SiO2. High temperature reduction further modifies the ratio of bridged to
linear CO on Pd–Ag surfaces. Since CO in bridged form is bound more strongly than linearly bound CO, this shift in adsorption geometry
modifies the apparent activation energy for ethylene hydrogenation. This work describes how restructuring of bimetallic Pd–Ag surfaces and
the presence of a co-adsorbed CO, work together to alter the reaction behavior of an industrially significant selective hydrogenation reaction.
# 2004 Elsevier B.V. All rights reserved.

Keywords: Ethylene hydrogenation; Activation energy; Pd–Ag bimetallic catalysts; In situ IR of adbsorbed CO; Catalyst restructuring of Pd–Ag

1. Introduction to ethane, since it represents a loss of valuable feedstock.

Acetylene is present as an impurity in ethylene produced
from a steam cracker. The selective hydrogenation of
acetylene in these cracking feedstocks is an important
industrial process for the purification of ethylene. Industrial
feedstocks for the production of ethylene polymers must
contain no more than 5–10 ppm of acetylene [1]. During
‘‘front-end hydrogenation’’, a large excess of hydrogen is
present along with the acetylene. The acetylene is converted
to ethylene, but it is important to prevent over hydrogenation
* Corresponding author. Tel.: +1 505 277 0477; fax: +1 505 277 1024.
E-mail address: datye@unm.edu (A.K. Datye).
Therefore, ethylene selectivity is a key objective, as is the
importance of avoiding thermal runaway for this exothermic
reaction. It is well known that palladium, promoted with
group Ib metals such as silver, and dispersed on a support
like alumina, is a catalyst that shows good activity and
selectivity for the reaction of acetylene hydrogenation [1].
In previous work from our group [2], we have shown that
structural changes induced in Pd/SiO2 and Pd–Ag/SiO2
catalysts by consecutive oxidation and reduction pretreat-
ments have a profound effect on catalyst activity and
selectivity. The catalyst oxidized in air at 500 8C was least
selective and produced the largest amounts of by-product
oligomers (green oil). High temperature reduction in H2

0926-860X/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.12.026
238 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
improved the selectivity of ethylene and also seemed to alter
the activation energy for ethylene hydrogenation. Since
ethylene hydrogenation is a well known structure-insensitive
reaction, it was not clear, why structure changes in the
catalyst should alter the activation energy for this reaction.
In the present study, we examine the role of structure
changes in Pd–Ag crystallites on the activation energy for
ethylene hydrogenation. As we show in this study, it is the
presence of co-adsorbed CO that modifies the apparent
activation energy for ethylene hydrogenation in response to
changes in surface structure. The reaction activation energy
determines the sensitivity of the catalyst to temperature
increase and hence may alter the tendency for thermal
runaway during selective hydrogenation of acetylene.
2. Experimental
Catalysts were prepared by impregnation using Pd(NO3)2
and AgNO3 solutions. The silica support used was 270 nm
Stober spheres, which are nonporous silica spheres prepared
by hydrolysis of TEOS under basic conditions [2]. The
monometallic catalyst had a nominal weight loading of 0.5%
of metal; the bimetallic catalyst has a nominal weight
loading of 0.5 wt.% of Pd and Ag for a total metal loading of
1 wt.%. After impregnation, the catalysts were calcined at
500 8C. Before reaction, the catalysts were pretreated in situ;
first to oxidize the catalyst at 500 8C in a mixture of O2 and
He (4 and 20 cc/min, respectively) for 2 h, and then reduced
in pure H2 (5 cc/min) at 500 8C (high temperature reduction
(HTR)) or 100 8C (low temperature reduction (LTR)) for
2 h. Also, the catalyst particles were sieved to a size between
50 and 100 mesh to obtain a particle diameter to reactor
diameter ratio between 1:12 and 1:20. This ensures proper
flow in the micro reactor and prevents channeling of the gas.
2.1. Reactivity measurements
The selective hydrogenation reaction was performed in a
fixed-bed quartz micro reactor with 25 mg of catalyst loaded
into the reactor and retained between quartz wool. The
catalyst was studied in its as-prepared state and after several
pretreatments. A premixed gas consisting of 35% C2H4,
0.5% C2H2, 1000 ppm CO and the balance N2 was obtained
from Scott Specialty Gases. The premixed gas (10 sccm)
was mixed with 2 sccm of ultra high purity (UHP) H2 to
complete the reaction mixture. For each reaction run, the
reaction was started at temperatures in which the initial
acetylene conversion was between 40 and 50%. The reaction
temperature was then increased to study the influence on
product distribution. Reactant gas continued to flow over the
catalyst for the duration of the run (approx. 2 h
15 min).
The clean up temperature is the temperature at which 99.3%
of acetylene in the feed has been converted (10 ppm
acetylene in effluent). After the clean up temperature, the
reactor temperature was increased at 5 8C intervals to allow
measurement of activation energy for ethylene hydrogena-
tion. At T > Tclean up, most of the acetylene has reacted and
hence we can measure the activation energy for ethylene
hydrogenation. By starting the reaction at a low temperature
and exposing all catalysts to the reaction mixture for about
2 h, we could ensure that all catalysts had comparable levels
of carbonaceous surface layers.
An on-line HP 5890 gas chromatograph was used to
analyze the composition of the reaction effluent. The
products were separated on a PLOT capillary column, CP-
Al2O3/Na2SO4 25 m  0.25 mm  4 mm, from Chrompack.
Only hydrocarbon products are detected by the flame
ionization detector; hence, selectivity and conversion were
based on analysis of the hydrocarbons alone.
The selectivity of Pd catalysts for ethylene hydrogenation
was defined as:
C2 H4 ðoutletÞ  C2 H4 ðinletÞ
Selectivity ¼
C2 H2 ðinletÞ  C2 H2 ðoutletÞ
To compare selectivity of different Pd catalysts, selectivity
was plotted against delta temperature (DT = reaction tem-
perature  clean up temperature). In this manner, the cat-
alysts are compared at comparable conversion of acetylene.
This is important, since selectivity for a series reaction is a
function of conversion.
In order to understand the effect of the presence of C2H2
and CO on the activation energy for ethylene hydrogenation,
additional reaction tests were performed with a reaction
mixture that did not contain C2H2 (35% C2H4, 1000 ppm CO
and balance N2, obtained from Scott Specialty Gases) and a
reaction mixture that did not contain either C2H2 or CO
(35% C2H4 and balance N2 also obtained from Scott
Specialty Gases). The selective hydrogenation reaction and
the pretreatment processes were performed following the
procedure described above. However, since no C2H2 was
present in this case, there is no clean up temperature. Instead,
the reaction was carried out for about 2 h, and then reaction
rate was measured as function of temperature with 5 8C
intervals at temperatures similar to those used for the
selective hydrogenation reaction. This ensures that the
catalyst is exposed to a similar environment in each case.
2.2. Infrared spectroscopy
Infrared measurements were obtained in transmission
mode using a Bio-Rad FTS-60A spectrometer. The catalyst
was pressed at 1000 psi into 25 mg wafers of catalyst. A
reaction flow cell [4] comprises the wafer sandwiched
between NaCl windows (using graphite gaskets) in a
stainless-steel mount. The reaction cell volume is approx.
0.5 ml; total flows of 16–20 ml/min were used. The gas
compositions were 20% H2 (balance He) for the reducing
gas and purge gas and 1.2% C2H2/18% H2 for the reaction
gas. Samples were reduced from room temperature to 70 or
400 8C with a ramp rate of 10 8C/min and held for 1 h. CO
adsorption measurements were taken at 50 8C, after 5 min of
 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
purge gas flow. CO was removed from the surface by
running the reaction mixture for 10 min followed by a
mixture of C2H2 and H2 in the absence of CO that effectively
removes the CO adsorbed on the Pd. This was the method
used to generate a CO-free surface prior to the next CO
adsorption experiment. Typical conversions of the samples
reduced at 70 8C were >98%, while those reduced at 400 8C
were 70–90% at 50 8C.
3. Results
3.1. Ethylene hydrogenation in ethylene–acetylene–carbon
monoxide mixtures
In a series reaction of the type A ! B ! C (where A
represents acetylene, B ethylene and C ethane); selectivity
for formation of B is dependent on the conversion of reactant
A. The selectivity on Pd catalysts is usually very high at low
conversion, but it decreases as we get to complete
conversion of reactant A. It is therefore necessary to
compare catalysts at similar conversions; this is possible by
plotting selectivity as a function of delta temperature
(DT = reaction temperature  clean up temperature). At the
clean up temperature, all catalysts have 99.3% conversion of
acetylene. Fig. 1a shows the ethylene selectivity on Pd/SiO2
as a function of temperature (clean up temperature for each
catalyst is shown by the filled symbols). Fig. 1b shows the
ethylene selectivity on Pd/SiO2 as a function of DT. Fig. 2a
and b present the same information for the bimetallic
catalyst. It can be concluded that the consecutive oxidation
and reduction pretreatments of the Pd catalyst had limited
influence on the activation energy for hydrogenation, when
compared against the results obtained for the Pd–Ag
catalyst. It should also be noted that the selectivity at clean
up is close to 0 or is negative in one case, implying that all of
the acetylene is being reacted to form ethane. In contrast,
Fig. 1. Ethylene selectivity as a function of (a) temperature and (b) as a function of delta temperature on Pd/SiO2 catalyst for reaction mixture containing C2H2,
C2H4, H2, CO and N2. Delta temperature is the difference between reaction temperature and clean up temperature (which is indicated by the filled symbol in
plot a).
239
with the Pd–Ag catalyst (Fig. 2b), we can see that the
selectivity is greater than 0.5 at clean up, implying that only
half of the acetylene has been hydrogenated to ethane. These
results show clearly the improvement in ethylene selectivity
due to the presence of Ag. An even more significant effect is
the decreased sensitivity to temperature. When comparing
Figs. 2b and 1b, we can see that at similar DT of 30 8C, the
selectivity on the Pd/SiO2 has dropped to 10. In contrast, at
this same DT of 30 8C, the selectivity on the Pd–Ag/SiO2 is
still better than 1 for the catalyst reduced at 500 8C.
Catalyst pretreatment has a major effect on selectivity for the
bimetallic, with the 500 8C reduced catalyst showing much
better selectivity (1.1) compared to the low temperature
reduced catalyst selectivity (2.5). Since all of the acetylene
has been consumed past the clean up temperature, these
differences in temperature sensitivity must be a result of
changes in apparent activation energy for ethylene hydro-
genation.
At the clean up temperature, all of the acetylene present
in the feed stream has been converted. Therefore, at
temperatures greater than the clean up temperature, the
primary reaction is that of B (ethylene) reacting to C
(ethane). Since ethylene is present in excess in the feed
(ethylene:acetylene = 70:1), we can assume that the con-
centration of ethylene under these conditions is nearly
constant. Hence, the rate of formation of ethane can be given
as:
rB ¼ k B  C B
rB is the rate of reaction of ethylene hydrogenation (also
equal to the rate of ethane formation); kB the apparent first
order reaction rate constant; CB the ethylene concentration.
After clean up temperature, the number of moles of
ethane produced corresponds to the same amount of moles
of ethylene consumed, a plot of ln(moles of ethane
produced/per gram of catalyst per second) versus 1/T gives
the activation energy and pre-exponential factor for the
240 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
Fig. 2. Ethylene selectivity as a function of (a) temperature and (b) delta temperature on Pd–Ag/SiO2 catalyst for reaction mixture containing C2H2, C2H4, H2,
CO and N2. The filled symbol in plot a indicates the clean up temperature.
ethylene hydrogenation reaction. The Arrhenius plots for
ethylene hydrogenation on the Pd/SiO2 and Pd–Ag/SiO2
catalysts are shown in Figs. 3 and 4. It is clear that the
presence of Ag causes a drop in the apparent activation
energy for ethylene hydrogenation. The effect of pretreat-
ment is not significant on the Pd/SiO2 catalyst (activation
energies are 27.7
0.6 and 26.8
0.6 kcal/mol, respec-
tively for the LTR and HTR catalysts). On the other hand, on
Pd–Ag/SiO2, there is a major influence of effect of
pretreatment in the activation energies (20.5
0.4 and
13.5
0.3 kcal/mol, respectively for the LTR and HTR
catalysts).
3.2. Ethylene hydrogenation in ethylene–carbon monoxide
mixtures
Following the same procedure used for the determination
of the activation energy for ethylene hydrogenation, we
measured the activation energy for ethylene hydrogenation
Fig. 3. Arrhenius plot for Pd/SiO2 catalyst, reaction mixture containing
C2H2, C2H4, H2, CO and N2.
with ethylene–carbon monoxide mixtures (35% C2H4,
1000 ppm CO and balance N2). The results show that for
the Pd/SiO2 catalyst, there is no significant influence of
pretreatment on the activation energy for ethylene hydro-
genation in the absence of acetylene (29.3
0.4 kcal/mol
for LTR pretreatment and 26.9
0.6 kcal/mol for HTR
pretreatment). However, when the Pd–Ag/SiO2 catalyst was
tested under similar conditions, the activation energy was
affected by pretreatment (25.5
0.5 kcal/mol for the LTR
pretreatment and 20
0.5 kcal/mol for the HTR pretreat-
ment). The amount of acetylene present is rather small (0.5
acetylene:35 ethylene) so the rate of ethane formation is
similar with and without acetylene.
3.3. Ethylene hydrogenation with no acetylene or CO
present
Ethylene hydrogenation was also performed in mixtures
that did not contain any acetylene or CO (35% C2H4 and
balance N2). The activation energy for ethylene hydrogena-
Fig. 4. Arrhenius plot for Pd–Ag/SiO2 catalyst, reaction mixture containing
C2H2, C2H4, H2 CO and N2.
 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
Fig. 5. Arrhenius plot for Pd/SiO2 catalyst, reaction mixture containing
C2H4 and N2.
tion was around 8
1.2 kcal/mol and there was no
significant difference between the activation energy on
Pd/SiO2 and Pd–Ag/SiO2 catalysts, as shown in Figs. 5 and
6. Furthermore, there was no significant effect of pretreat-
ment on both the monometallic as well as the bimetallic
catalysts. As expected, the rate of ethylene hydrogenation
was much higher when CO was absent, since CO acts as a
poison for this reaction.
3.4. In situ infrared characterization of the catalysts
Figs. 7 and 8 show the spectrum of adsorbed CO on a Pd/
SiO2 catalyst reduced at 70 and 400 8C. CO is adsorbed first
in bridged CO species at low coverage with a peak maximum
of 1893 cm1. The peak maximum shits to higher
frequencies with increasing coverage of CO. While bridged
CO is the only species detected at low coverage, at higher
coverage linearly adsorbed CO also starts to appear with a
peak maximum near 2050 cm1. The spectra for Pd/SiO2
Fig. 6. Arrhenius plot for Pd–Ag/SiO2 catalyst, reaction mixture containing
C2H4 and N2.
241
Fig. 7. IR difference spectra before and after CO addition for Pd/SiO2
catalyst reduced at 70 8C: (a) 1 pulse, (b) 2 pulses, (c) 3 pulses, (d) 10 pulses,
(e) 5 min 101 ppm CO and (f) 1 min 190 Torr CO. The catalyst was
preconditioned under a C2H2/H2 reaction mixture for 10 min at 50 8C prior
to CO adsorption.
catalyst reduced at 400 8C are similar to those for Pd/SiO2
catalyst reduced at 70 8C with the distribution of linear and
bridged CO species almost unaffected by the higher
reduction temperature. The absorbance of the CO band is
reduced by a factor of 10 at the higher reduction
temperature, suggesting that metal particles sinter during
this exposure to higher reduction temperature [2]. Sub-
sequent oxidation and reduction treatments do not cause
further changes in metal surface area, as seen also from the
reversibility in the activity of these catalysts subjected to
multiple oxidation–reduction cycles [2].
Fig. 9 shows the CO adsorption spectrum of Pd–Ag/SiO2
catalyst reduced at 70 8C. The behavior in the bridged region
is similar to that of the Pd/SiO2 catalyst, but the fraction of
CO in the form of linearly bonded CO is enhanced by the
presence of Ag. In addition, the spectra appear broader in the
Fig. 8. IR difference spectra before and after CO addition for Pd/SiO2
catalyst reduced at 400 8C: (a) 1 pulse, (b) 6 pulses, (c) 10 pulses, (d) 5 min
101 ppm CO and (e) 1 min 190 ppm CO. The catalyst was preconditioned
under a C2H2/H2 reaction mixture for 10 min at 50 8C prior to CO adsorp-
tion [2].
242 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
Fig. 9. IR difference spectra before and after CO addition for Pd–Ag/SiO2
catalyst reduced at 70 8C: (a) 6 pulses, (b) 10 pulses, (c) 14 pulses, (d) 5 s
101 ppm CO, (e) 5 min 101 ppm CO and (f) 1 min 190 Torr CO. The
catalyst was preconditioned under a C2H2/H2 reaction mixture for 10 min at
50 8C prior to CO adsorption [2].
Fig. 10. IR difference spectra before and after CO addition for Pd–Ag/SiO2
catalyst reduced at 400 8C: (a) 1 pulse, (b) 5 pulses, (c) 10 pulses, (d) 5 min
101 ppm CO and (e) 1 min 190 Torr CO. The catalyst was preconditioned
under a C2H2/H2 reaction mixture for 10 min at 50 8C prior to CO adsorp-
tion [2].
bridged region, suggestive of larger heterogeneity in the Pd/
Ag sample. Fig. 10 shows the CO adsorption spectrum of a
Pd–Ag/SiO2 catalyst reduced at 400 8C; for this sample,
there is a significant increase in the intensity of linearly
bonded CO. The absorbance is reduced by a factor of 10
similar to that for the Pd/SiO2, suggesting that sintering is
affecting both samples [2].
4. Discussion
Table 1 summarizes the reported values for activation
energy of ethylene hydrogenation over a variety of catalysts
and reaction conditions including our results in this study.
Table 2 summarizes the activation energy values obtained
for ethylene hydrogenation in presence of CO as a function
of catalyst pretreatment. The values of activation energy
reported in the literature for the ethylene hydrogenation
reaction vary from around 5–12 kcal/mol [3,5–13]. Our
results show that the activation energy for ethylene
hydrogenation is about 8 kcal/mol, which is in agreement
with the literature. The activation energy increases in the
presence of CO, as seen in the present study as well as the
work of Chen et al. [6]. With CO and acetylene present, the
activation energy was even higher. Activation energy was
further affected by catalyst pretreatment, as seen in Table 2.
As we discuss below, the higher apparent activation
energy for ethylene hydrogenation is caused by the presence
of the co-adsorbates CO and acetylene. The influence of
pretreatment is explained by changes in the surface structure
of the Pd catalyst as Ag breaks up ensembles of Pd atoms.
No influence of pretreatment is seen in the case of
monometallic Pd catalysts because any oxidative rough-
ening of Pd does not affect the behavior of ethylene
hydrogenation, which is a structure-insensitive reaction. In
contrast, for n-butane hydrogenolysis, a structure sensitive
reaction, we have shown previously how oxidative rough-
ening of Rh can lead to increased activity and altered
selectivity [14].
Reaction kinetics during selective acetylene hydrogena-
tion is determined by competition between co-adsorbed
acetylene, CO and ethylene. This was shown clearly in the
work of Cider and Shoon [15] for ethylene hydrogenation
over Pd/a–Al2O3. When acetylene was introduced in small
pulses to a feed stream containing ethylene, hydrogen and
carbon monoxide, the catalyst surface responded very
quickly to this pulse, generating a large increase in the
carbon monoxide level in the outflow stream for the duration
of the pulse and a rapid formation of ethane immediately
following the acetylene pulse. From this observation, it is
clear that CO prevents ethylene hydrogenation, since it is
bound more strongly to the surface than ethylene. When
acetylene is pulsed into this system, it displaces CO opening
up sites where hydrogenation can occur and leading to the
formation of ethane. Hence, the activation energy for the
hydrogenation of ethylene in the presence of acetylene and
CO must consider the site blocking effects of these co-
adsorbates. The activation energy for the reaction then is
equal to the heat of desorption of these co-adsorbates. As we
show below, changes in surface structure caused by
rearrangements of Ag on the Pd surface affect the reaction
dynamics and lead to the observed changes in apparent
activation energy for ethylene hydrogenation.
Assuming that the surface reaction of ethylene is the
controlling step of the mechanism and that the adsorption of
ethylene, hydrogen and carbon monoxide takes place on the
same kind of active site, the following rate equation is
obtained by applying a Langmuir–Hinshelwood–Hougen–
Watson (L–H–H–W) kinetic analysis:
 
Cc
k  Ca  Cb 
K
ra ¼ (1)
1 þ Ka  Ca þ Kb  Cb þ Kc  Cc þ Ki  Ci
 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245 243

Table 1
Summary of activation energies for the reaction of ethylene hydrogenation over a variety of catalysts and reaction conditions
Activation energy (kcal/mol) Temperature range (K) Catalyst Reactants Reference
6.4 408–462 5% Ni/SiO2–Al2O2 C2H4 + H2 [3]
8.6 272–262 1.2% Pt/SiO2 C2H4 + H2 [5]
6.9 272 Pd/Al2O3 C2H4 + H2 [7]
9.9 257–655 1% Pt/Al2O3 C2H4 + H2 [8]
10 170–206 Pt wire C2H4 + H2 [9]
10.8 272–248 Pt (1 1 1) C2H4 + H2 [10]
8.8 212–272 2% Pt/Al2O2 C2H4 + H2 [11]
9.1 200–222 0.5% Pt/SiO2 C2H4 + H2 [12]
10 200–400 Pt (1 1 1) C2H4 + H2 [6]
20.5 200–299 Pt (1 1 1) C2H4 + H2 + CO [6]
26 350–480 0.5% Pd/SiO2 C2H4 + H2 + C2H2 + CO Present work
12–21 350–480 0.5% Pd–Ag/SiO2 C2H4 + H2 + C2H2 + CO Present work

Where k is the kinetic reaction constant; Kb, Kc and Ki the
adsorption constants for hydrogen, ethane and carbon mon-
oxide, respectively, and Ca, Cb, Cc and Ci the concentrations
of ethylene, hydrogen, ethane and carbon monoxide (the
inert i), respectively.
In order to simplify the rate equation, we will first assume
that carbon monoxide covers most of the catalyst surface and
that Ki  Ci all of the other adsorption terms in the
denominator. Then, Eq. (1) is transformed into:
 
Cc
kapparent  Ca  Cb 
K
ra ¼ (2)
Ci
where kapparent = k/Ki.
kapparent ¼ A  expððEactivation for hydrogenation
 DHadsorption CO ÞÞ
Eactivation apparent ¼ Eactivation for hydrogenation
 DHadsorption CO
where Eactivation corresponds to the activation energy for the
surface reaction of ethylene hydrogenation and DHadsorption
corresponds to the heat of adsorption of carbon monoxide on
the active site. Changes in observed activation energy can now
be related to changes in the heat of adsorption of CO caused by
surface structure changes induced by pretreatment.
Several studies have discussed the adsorption behavior of
carbon monoxide on the surfaces of single crystal and
polycrystalline Pd films [16,17]. Supported Pd catalysts
have been discussed in terms of support and pretreatment
effect, crystallite size effect [18–21] and alkali metal (Li,
Na, K) promotion effects on Pd/SiO2 catalysts [22]. Some of
these data do not distinguish between the heat of adsorption
of bridge and linear carbon monoxide species: Dropsch and
Baerns [21] reported values between 22 and 25 kcal/mol for
Pd/SiO2 with different Pd loadings, Chou and Vannice [18]
reported values between 28.5 and 25.6 kcal/mol for Pd/SiO2
with different Pd loadings and under different pretreatments.
Guerrero-Ruiz et al. [20] distinguished three different types
of carbon monoxide adsorbed; a multibonded carbon
monoxide formation on two-fold site of Pd (1 1 1) planes
with adsorption heat values around 47 kcal/mol; a second
type of adsorbed species (bridge type) at adsorption heat
values lower than 42 kcal/mol and a third type of species
(linear type) formed at adsorption heat values lower than
22 kcal/mol. Delaurent et al. [19] reported just bridge and
(3) linear species but recognized the effect of surface coverage,
the bridge species having a heat of adsorption between 40
and 18 kcal/mol for low and high surface coverage,
respectively, and the linear species having a heat of
(4)
adsorption between 22 and 12 kcal/mol for low and high
surface coverage, respectively.
Our in situ infrared studies of carbon monoxide
adsorption showed that the presence of Ag in the Pd/SiO2
strongly decreased the amount of bridged form of carbon
monoxide and increased the proportion of linear carbon
monoxide relative to the bridged form (Figs. 9 and 10). The
effect was even more pronounced after high temperature
reduction in H2, probably as a result of Ag breaking up Pd
ensembles. Since the carbon monoxide in bridged form is
more strongly adsorbed than the linear one, these changes in

Table 2
Apparent activation energy for ethylene hydrogenation with CO present in the reaction mixture (kcal/mol)
Reaction mixture Pd/SiO2 Pd–Ag/SiO2
With acetylene Without acetylene With acetylene Without acetylene
Pretreatment
100 8C 27.7
0.6 29.3
0.4 20.5
0.4 25.5
0.5
500 8C 26.8
0.6 26.9
0.6 13.5
0.3 20.0
0.5
244 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245
the form of adsorbed CO can change the heat of desorption
of CO.
Carbon monoxide is displaced from the catalyst surface,
when acetylene is pulsed into a reaction feed stream
containing ethylene and CO, as shown in the work of Cider
and Shoon [15]. It can be inferred that the carbon monoxide
species that desorb first would be the ones that are more
weakly attached to the catalyst (linear type), followed by the
bridge form and finally, the multibonded carbon monoxide.
Based on our in situ infrared studies of CO adsorbed on Pd/
SiO2, the dominant carbon monoxide adsorbed species is the
bridged form. A corrected value for the true activation
energy of ethylene hydrogenation of 9
1 kcal/mol is
obtained after subtracting the heat of adsorption (based on
Eq. (4)) of the adsorbed bridge carbon monoxide species
from the apparent activation energy values calculated for the
low and high temperature pretreatment (27.7
0.6 and
26.8
0.6 kcal/mol, respectively). This value is in good
agreement with the value reported for the ethylene
hydrogenation reaction in absence of carbon monoxide
(between 6 and 10 kcal/mol) [5,6]. The activation energy
values obtained from the reaction tests for feed mixtures
with and without acetylene are very similar, as summarized
in Table 2.
The activation energy results for the Pd–Ag/SiO2 catalyst
differ from the monometallic Pd/SiO2 in two significant
ways. First, there is a drop in activation energy for ethylene
hydrogenation after high temperature treatment in H2.
Second, the activation energy is lower in feed streams
containing acetylene. It should be noted that our measure-
ments are performed in an integral reactor; hence, even
though the acetylene is consumed completely by the outlet
of the reactor, acetylene hydrogenation is occurring prior to
ethylene hydrogenation over the entrance region of the
catalyst bed. It is clear that the activation energy of this
reaction is the result of the combination of the activation
energy of ethylene hydrogenation on free active site plus the
heat of adsorption of carbon monoxide that should be
removed form the surface to allow the ethylene to react
(Eq. (4)). In the case of the Pd–Ag/SiO2 catalyst, CO is
present in bridged as well as linear forms. For Pd–Ag/SiO2,
the in situ infrared study revealed that there is no single
carbon monoxide dominant species absorbed on the catalyst;
however, there is a strong decrease in the amount of bridged
carbon monoxide and an increase in the proportion of linear
carbon monoxide relative to the bridged form (especially
after high temperature reduction). It has been suggested that
in high surface coverage condition (probably the conditions
encountered during reaction), only the weaker linear form
can be easily desorbed, with a consequent decrease in the
heat of desorption [22–25]. Hence, our observed values of
activation energy of 20 kcal/mol after LTR are consistent
with the lower heat of adsorption of CO in linear form. Chen
et al. [6] report that the activation energy of ethylene
hydrogenation on Pt in the presence of carbon monoxide is
about 20.5 kcal/mol, while the activation energy in the
absence of carbon monoxide is 10 kcal/mol. Experimentally,
we also see an increase in activation energy for ethylene
hydrogenation, when there is no acetylene present in the
feed stream. Therefore, we suspect that the presence of
acetylene changes the distribution of carbon monoxide
species absorbed under reaction conditions.
These results show that controlling the way carbon
monoxide absorbs on the catalyst affects the activation
energy for over hydrogenation of ethylene in acetylene–
ethylene–H2 mixtures. While the CO hydrogenation reac-
tion, by itself, is structure-insensitive, the adsorption of CO
is strongly affected by surface structure changes. These
changes in CO adsorption can modify the reaction behavior
in this system. Since thermal runaway of such exothermic
reactions is a serious concern, knowledge of how the
activation energy changes with catalyst structure would be
important for proper operation of selective hydrogenation
reactions.
5. Conclusions
Oxidation–reduction pretreatments do not appear to
influence the selectivity of acetylene hydrogenation to
ethylene on Pd/SiO2 catalyst; however, when Ag is present
with the Pd, the higher temperature reduction improves the
reaction selectivity and reduces the activation energy for Pd–
Ag/SiO2. IR spectra of adsorbed CO show that the presence
of Ag affects the bonding of CO, favoring linear CO over the
bridged forms, this effect being even more pronounced after
higher temperature reduction in H2. In this work, we have
carefully measured the activation energy in ethylene
hydrogen mixtures containing acetylene as well as CO.
The role of the CO is to increase the activation energy for the
reaction, consistent with the simple model that CO must
desorb for ethylene hydrogenation to occur. The role of
acetylene is more complicated, since it can modify the CO
adsorption geometry, and can also displace some of the CO.
We observe a drop in activation energy in the presence of
acetylene, but only on Pd–Ag catalysts, with no effect on Pd
only catalysts. In summary, we have shown how surface
restructuring of Pd–Ag surfaces is possible due to oxidative
pretreatments, and these structural changes can modify the
reaction behavior of these catalysts during selective
hydrogenation of acetylene.
Acknowledgments
We acknowledge with pleasure the support for this work
from the Department of Energy, Office of Science, via Grant
DE-FG02-98ER14917, PAIR (Partnership for Academic
Industrial Research). This research was also supported, in
part, by the Dow Chemical Company. We also thank
Michael Holbrook, Joe Maj, and John Blackson at Dow
Chemical Company for helpful discussions.
 H. Zea et al. / Applied Catalysis A: General 282 (2005) 237–245 245

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