catalysts

Article
Kinetic Study of the Selective Hydrogenation of
Acetylene over Supported Palladium under
Tail-End Conditions
Caroline Urmès 1,2 , Jean-Marc Schweitzer 2 , Amandine Cabiac 2 and Yves Schuurman 1, *
1 IRCELYON CNRS, UMR 5256, Univ Lyon, Université Claude Bernard Lyon 1, 2 avenue Albert Einstein,
69626 Villeurbanne Cedex, France; caroline.urmes@gmail.com
2 IFP Energies nouvelles, Etablissement de Lyon, Rond-point de l’échangeur de Solaize, BP3, 69360 Solaize,
France; jean-marc.schweitzer@ifpen.fr (J.-M.S.); amandine.cabiac@ifpen.fr (A.C.)
* Correspondence: yves.schuurman@ircelyon.univ-lyon1.fr; Tel.: +33-472445482




Received: 9 January 2019; Accepted: 31 January 2019; Published: 14 February 2019


Abstract: The kinetics of the selective hydrogenation of acetylene in the presence of an excess
of ethylene has been studied over a 0.05 wt. % Pd/α-Al2 O3 catalyst. The experimental reaction
conditions were chosen to operate under intrinsic kinetic conditions, free from heat and mass transfer
limitations. The data could be described adequately by a Langmuir–Hinshelwood rate-equation
based on a series of sequential hydrogen additions according to the Horiuti–Polanyi mechanism.
The mechanism involves a single active site on which both the conversion of acetylene and ethylene
take place.

Keywords: power-law; Langmuir–Hinshelwood; kinetic modeling; Pd/α-Al2 O3

1. Introduction
Ethylene is the largest of the basic chemical building blocks with a global market estimated at
more than 140 million tons per year with an increasing growth rate. It is used mainly as precursor for
polymers production, for instance polyethylene, vinyl chloride, ethylbenzene, or even ethylene oxide
synthesis. New ways of production of ethylene are emerging, such as ethanol dehydration, but steam
cracking of naphtha and gas remains the major producer of alkenes. The C2 fraction at the outlet of a
steam cracker contains mainly ethane and ethylene, but also traces of acetylene. These trace amounts
need to be removed as acetylene is known to poison the Ziegler–Natta catalyst that is used for the
polymerization of ethylene. This important issue is done by selective hydrogenation of acetylene,
important process in petrochemical industry. Thus, the initial acetylene content, approximately
0.8–1.6%, needs to be reduced to less than 5 ppmv for chemical grade and less than 1 ppmv for
polymer grade ethylene. Depending on plant design, selective hydrogenation is carried in two
different ways: front-end and tail-end [1]. In the tail-end configuration, which corresponds to 70% of
all units worldwide, the process is placed after CH4 and H2 separation. The hydrogen is added in an
amount slightly higher than the acetylene concentration and the majority of the stream is ethylene [1,2].
In front-end configuration, the selective hydrogenation unit is placed upstream of the demethanizer
and a larger amount of hydrogen is available (around 20%).
Alumina-supported palladium or bimetallic palladium-silver catalysts are used for this process,
assuring very high activity and selectivity for acetylene hydrogenation. The main goal is to reduce
the acetylene content without the hydrogenation of ethylene to ethane. Catalyst deactivation by coke
formation is very common under tail-end conditions as is the formation of C4 byproducts.
The kinetics of this reaction have been the subject of several studies [3–9] and have been analyzed
in detail by Borodziński and Bond [8]. The most elaborate models consist of 2 or 3 distinct sites, each

Catalysts 2019, 9, 180; doi:10.3390/catal9020180 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 180 2 of 13

catalyzing a specific reaction [8]. In the case of multiple active sites, a small and a large size site are
considered. Small sites favour the adsorption and selective hydrogenation of acetylene to ethylene,
whereas the adsorption of ethylene seems to be only possible on the large sites. Pachulski et al. [9], in a
systematic study of acetylene hydrogenation over Pd-Ag/Al2 O3 , evaluated 77 different rate equations
and found that the best rate equation was based on two different sites.
However, few studies discriminate between different models and in some cases, the need for
a more elaborate mechanism might be due to additional factors such as the addition of carbon
monoxide or the use of a catalyst promotor. For example, Bos et al. [6] discarded a single-site
Langmuir–Hinshelwood mechanism because of its inability to predict the observed change of the
ethane selectivity when carbon monoxide was added to the feed. An alternative explanation can
be that addition of carbon monoxide actually creates an additional site by either an electronic or
geometric effect.
In this study, we derived rate equations based on a sequence of elementary steps. Several rate
equations were obtained depending on the assumption of the rate-determining step. A regression
analysis was then performed to select the most appropriate mechanism based on our experimental
data and to estimate the rate parameters.

2. Results
An analysis of the repeatability of the experiments has been performed. Several operating
conditions have been tested at both temperatures:

- Operating conditions 1: yC2 H2 = 1.0%; y H2 = 4.3%; yC2 H4 = 70% and y Ar = 24.7%

- Operating conditions 2, 51 ◦ C: yC2 H2 = 0.6%; y H2 = 4.3%; yC2 H4 = 70% and y Ar = 25.1%
- Operating conditions 2, 62 ◦ C: yC2 H2 = 0.8%; y H2 = 4.3%; yC2 H4 = 70% and y Ar = 24.9%

Each operating condition was tested three times per catalyst loading. Two catalyst loadings
were used. All this data was used to calculate the relative standard deviations of both the acetylene
conversion and the ethane exit molar flow rate. The relative standard deviations are given in Table 1.
Rather large (10–20%) relative standard deviations were found for the molar exit flows of ethane.

Table 1. Relative standard deviation (rsd) of 6 repeated experiments (3 for each catalyst loading, 2
loadings) for both conversion and ethane outlet flow at 2 conversion levels.

Operating Operating Operating Operating

Conditions 1 Conditions 2 Conditions 1 Conditions 2
T (◦ C) XC2H2 rsd (%) XC2H2 rsd (%) FC2H6 rsd (%) FC2H6 rsd (%)
51 0.13 9.3 0.36 6.2 0.07 19 0.13 11
62 0.23 7.8 0.37 8.5 0.11 16 0.16 15

The variation of the relative flows of acetylene, ethylene, hydrogen, and argon allowed
determination of the apparent reaction orders with respect to acetylene, ethylene, and hydrogen.
Apparent reaction orders are based on power law expressions for the rates as follows:

β
− rC2 H2 = k1 PCα21 H2 PH12 PCγ21H4

β γ
rC2 H6 = k2 PCα22 H2 PH22 PC22H
4

As no C4 products were experimentally observed, the kinetic analysis is restricted to the

hydrogenation of acetylene to ethylene and ethylene to ethane. Both rate equations were integrated
numerically and the reaction orders were determined by regression analysis of the acetylene conversion
and the molar exit flow rate of ethane of the data set at each temperature separately. The estimated
values of the reaction orders are given in Table 2.
 1 (C2H2) β1 (H2) 1 (Cγ2H
1 (C 22) (C2H2γ) 1 (C2H
2) 2H4) β1 (H β42)(H2) 2 (Cγ22H(C
2) 2H4) β2 (H2) γ2 (C2H4)
Catalysts 2019, 9, x FOR51 PEER REVIEW
−0.88 ± 0.09 1.46 51 ± 0.16 −0.88−0.13
± 0.09± 0.071.46 ±−1.00
0.16 ± 0.20
−0.13 ±1.42 0.07± 0.70
−1.001.09 3±of0.50
± 0.20 13 1.42 ± 0.70 1.09 ± 0.50
Catalysts 2019, 9, x FOR PEER REVIEW 3 of 13
62 −0.93 ± 0.07 1.49 62 ± 0.34 −0.93−0.19
± 0.07± 0.041.49 ±−1.56
0.34 ± 0.13
−0.19 ±1.69 0.04± 0.88
−1.560.30 ± 0.13
± 0.151.69 ± 0.88 0.30 ± 0.15
Catalysts 2019, 9, x FORPEER REVIEW β1 (H2)
1 (C2H2) γ1 (C2H4) 2 (C2H2) β2 (H2) γ2 (C2H4) 3 of 13
Catalysts 2019, 9, x FOR
Catalysts
51 A −0.88 1PEER
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2019, 2H
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3 of 13 3 of 13
Catalysts 2019, 9, x FOR negative
PEER REVIEW
1 (C2H2)
reaction
β 1 (H2)
order
negative
γfor acetylene
reaction
1 (C2H4)  was 0.20
order
2 (C2H2)
1.42
observed,
for acetylene
β
±−0.9
2 (H2)
0.70 was1.09
with
γ
0.50
observed,
respect
2 (C2H4)
to−0.9
3 of 13 acetylene
with respect to acetyl
51 −0.88
629, x FOR−0.93 ±±0.09
0.07 1.46
1.49 ±±0.16 −0.13
0.34 with
−0.19 ±±0.07
0.04 to−1.00
−1.56 ±±0.20
0.13 1.42
1.69 ±±0.70
0.88 1.09
0.30 ±±formation.
0.50
0.15 3 ofto13 aThis
Catalysts 2019,
51 1PEER
consumption,
−0.88(C±2H and
REVIEW
2)
0.09
(−1)–(−1.5)
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β1 (H
1.46 ± 2)
0.16
and
γ1 (C
−0.13
respect
± )
0.07 2ethane
2H4(−1)–(−1.5)
−1.00 (C±2Hwith
2) formation.
0.20
respect
β2 (H
1.42 ± 2to
) This
0.70
ethane
γ2correspond
1.09 (C±2H 4)
0.50
strong
correspond to a stro
62 −0.93 ± 0.07 1.49 ± 0.34 −0.19 ± 0.04 −1.56 ± 0.13 1.69 ± 0.88 0.30 ± 0.15 3 of 13
Catalysts 2019, 9, x
511 (C2of
FOR
adsorption PEER REVIEW
HTable
2) 2.βEstimated
acetylene
−0.88 (Hon2) the values
1adsorption
± γof
1 (C
surface 2H 4)the
acetylene
of of
the 2 (C
catalyst.
on
reaction the 2H 2) with
surface
This
orders βtheir
order
of (His295%
2 the )catalyst.
lower γthan
2 (C 2H
This
confidence the)order
valuesis lower
4intervals. reported
thaninthe values reported
62 −0.93 ± 0.09
0.07 order 1.46
1.49 ± 0.16
± for
0.34acetylene −0.13
−0.19 ± ± 0.07
0.04 −1.00 −1.56 ±
± 0.20
0.13 −0.9 1.42
1.69with ±
± 0.70
0.88 1.09 0.30 ± ±to 0.50
0.15
A51negative
the literature
−0.88 1reaction
(C0.09
± 2Hfor2) acetylene
1.46 β±1 0.16
the (H 2)consumption,
literature −0.13 γ1for (C0.07
± Hwas 4)which
2acetylene
−1.00 2are
observed, (C0.20 2H
consumption,
± 2)
between 1.42 (H2) respect
β±0–(−0.7)
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0.70 are γ2between
[7,10–14]
1.09 ± (C 0.50 )acetylene
2H4depending 0–(−0.7) on [7,10–14]
the depending on
62 −0.93 ± 0.07 1.49 ± 0.34 −0.19 ± 0.04 −1.56 ± 0.13 1.69 ± 0.88 0.30 ± 0.15
A
consumption, negative
51 and
−0.88reaction
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± H
(−1)–(−1.5)
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1.46 β 1 (H
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ethane
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This
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)a strong
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T (reaction
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± 0.34 for −0.19 ± 0.04
acetylene was −1.56 observed, ± 0.13 −0.9 1.69 ± with 0.88 respect 0.30 ± 0.15
consumption,
adsorption 51
62 ofThe and
−0.88
acetylene
−0.93 (−1)–(−1.5)
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0.07 αthe
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A
consumption, negative and reaction
(−1)–(−1.5) order with acetylene
respect to was
ethane observed,
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correspond to
to acetylene
a strong
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theA literature 62 of acetylene
−0.93
for ±
acetylene on
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are This
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±
[7,10–14]0.88 the values
0.30
depending ± reported
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the
consumption, However,
negative and 51 the
reaction same
(−1)–(−1.5) 0.88
order range for
with 0.09
However, ofacetylene
magnitude
respect the ±
1.46 same to0.16
was wasrange
ethane −found
observed, 0.13 of ±
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Aduriz 1.00
withwas
and ±correspond
0.20
found
al.: 1.3–1.6
respect 1.42
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[10], a but
acetylene and
strong 1.09
under ± 0.50
al.: 1.3–1.6
front- [10], but under fro
adsorption
the literature of acetylene
for 62 acetylene on−the surface
consumption,
± of 1.49thewhich catalyst.
± are This between
− order± is lower
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[7,10–14]
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the
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for acetylene 0.34 was 0.19
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the literature end ofandconditions.
acetylene (−1)–(−1.5)
for acetylene onMost the withend
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surface
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conditions.
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the which
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order
are studies
This of
between
formation.
+1order [6,11,12].
report is lower
0–(−0.7)
This
an Molero order correspond
than
[7,10–14] ofthe
et+1 al. to reported
[6,11,12].
observed
values
depending
a strongMolero
aonreaction inet al.order
the observed a reaction or
conditions.
AThe
consumption, negative
order and reaction
for hydrogen,
(−1)–(−1.5) order with for respect
approximately acetylene to 1.5, was
ethane is observed,
high formation. and −0.9
hard This with
toacetylene respect
explain
correspond toto acetylene
mechanistically. a for strong
adsorption
the of hydrogen
acetylene between
on the surfaceof
1–1.25,
hydrogen
of depending
the
literature for acetylene consumption, which are between 0–(−0.7) [7,10–14] depending on the between
catalyst. onThis 1–1.25,
the ordertemperature
depending
is lower for on
than the
the temperature
values hydrogenation
reported acetylene
in over ahydrogenation
Pd over a
conditions.
consumption,
However, The order the and
samefor (−1)–(−1.5)
hydrogen,
range of magnitude approximately
with respect was to1.5,
found ethane isThis
by high
Adurizformation. and and hard al.:This to
1.3–1.6 explain
correspond [10], mechanistically.
but to
under a strong front-
theadsorption
literature foil of
for acetylene
[7]. A acetylene
From
negative aon the
reaction surface
consumption,
careful foil
analysis[7].
order of
From
forthe
which
of catalyst.
thea
acetylene are
careful
data, between
wasthey
analysis order
derived
observed, 0–(−0.7)
of isthe lower
−
that data,
0.9 the than
[7,10–14]
with they the
hydrogen
respect values
depending
derived toreaction reported
that
acetylene on the the
order in can vary
hydrogen
consumption, reaction order can v
conditions.
However, The order the same for range
hydrogen, of approximately
magnitude was found 1.5, by isThis high
Aduriz and and hard al.: to
1.3–1.6 explain [10], mechanistically.
but under front-
adsorption
end
the conditions.
literature of acetylene
for Most
acetylene on
studies the surface
report
consumption, anof the
order which catalyst.of +1 are [6,11,12].
between order Molero is
0–(−0.7) lower et al.than the
observed
[7,10–14] values a
depending reported
reaction on order in
the
conditions.
However, The betweenand
order
the for −for
(same values
1)–( −1.5)ofof
hydrogen,
range with1magnitude
and between
respect 1.5. Excess
approximately tovalues
wasethane foundhydrogen
of 1 and
formation.
1.5, is Aduriz
by high1.5.
canThis Excess
remove
and and hydrogen
correspond
hardal.: stronglyto explain toadsorbed
can
a[10], remove
strong carbonaceous
strongly
adsorption
mechanistically. ofadsorbed
species carbonaceous spec
acetylene
end
the
of The conditions.
literature
hydrogen
conditions. betweenMost
acetylene studies
1–1.25, report
consumption,
depending an order onwhich the of +1 are [6,11,12].
temperature betweenMolero for0–(−0.7)
acetylene et 1.3–1.6
al. observed
[7,10–14] hydrogenation
but
a reaction
depending under
over on front-
order
athePd acetylene
However, order
from
on the
the same for
the hydrogen,
catalyst
surface of surface
the approximately
from
catalyst. and the so catalyst
This createsorder 1.5, is is
surface
free lower high
surface and than and sosites. hard
creates
the values to
free explain
surface
reported mechanistically.
in sites.
the literature for
end
of conditions. Mostrange studies of magnitude
report an order was found of +1 by Aduriz
[6,11,12]. Molero and al.: et 1.3–1.6
al. observed [10], but a reaction under front- order
foilhydrogen
conditions.
However, [7].
Thethe From
order between
same a careful
for
Regarding
consumption, range
1–1.25,
analysis
hydrogen,of the
which
depending
magnitude
rate are ofofbetween
the
approximately data,
was
Regarding
consumption
on the
found
0–( they − the
temperature
1.5,
0.7)derived
by
ofrateisAduriz
acetylene,
[7,10–14] high
of that for
and
and
consumption the
no
acetylene
depending hydrogen
hard
al.:strong 1.3–1.6toon
of
hydrogenation
effect reaction
explain
[10],
acetylene,
the is but
observed
conditions. order
mechanistically.
under
no strong
overcan
front-
for
avary
Pd
effect
ethylene. is observed
The for ethylene. T
end
of conditions.
hydrogen between Most studies
1–1.25, report
depending an order
on the of +1 [6,11,12].
temperature Molero
for acetylene et al. observed
hydrogenation a reaction over order
a Pd
foil
between
However, [7]. From
The order order
values
the a careful
samefor
of 1 and
range analysis
hydrogen, 1.5.
of Excess
magnitudeof the
approximately data,
hydrogenwas they
found 1.5,
can derived is
remove
by high
Aduriz that and the
strongly and hydrogen
hard al.: to
adsorbed
1.3–1.6 reaction
explain carbonaceous
[10], but order
mechanistically.
under can speciesvary
front-
endof conditions.
hydrogen is close
Most
The
between studies
order to for
1–1.25,zero as
report order
hydrogen,
dependingshownan isorder close
by onnumerous
approximately of to+1
the zero asstudies
[6,11,12].
temperature shown
1.5, isMolero
high[12].
by acetylene
for numerous
and However,
et hard al. observed to studies
some
explain
hydrogenation aethylene
[12].
reaction However,
mechanistically. adsorption
over order avaryPd some occurs
ethylene adsorption occ
However,
foil
between
However, [7]. From the asame
values careful
ofsurface
1range
and analysis
1.5. Excess
of magnitude of thehydrogen data,wasthey found can derived
remove
by Aduriz that the
strongly andhydrogen al.: adsorbed
1.3–1.6 reaction
carbonaceous
[10], but order under can species
front-
from
ofend
hydrogen theas
conditions. catalyst
thebetween
indicated
same Most range studies
1–1.25,
by the
ofand so
report
depending
small
magnitude as creates anwas
indicated
negative on free
order the
value
by
found surface
of the +1
temperature
of small
by thesites.
[6,11,12].
Aduriz reaction
negative for Molero
and acetylene
order.
value
al.: et
1.3–1.6Foral.hydrogenation
of theobserved
ethane reaction
[10], but aorder.
formation,
under reactionover For
the
front-end a order
Pd
reaction
ethane formation,
order
conditions. the reaction or
foil
between [7]. From a careful analysis of the data, they derived that the hydrogen reaction order can vary
from
end
of the values
conditions.catalyst
Regarding
hydrogen between
ofsurface
Most
the
1 and
ratestudies 1.5. Excess
and
of
1–1.25, so creates
report
consumption
depending
hydrogen
an free
order
onof surfaceof
acetylene,
the
can +1 remove
temperaturesites.
[6,11,12]. no
strongly
strong Molero
for effect
acetylene
adsorbed
et al.
is observed
observed
carbonaceous
hydrogenation a
for reaction
ethylene. over
species
order
a The
Pd
foil [7]. From
between in
Most
values ethylene
a careful studies
ofsurface
1 andis much
analysis
report higher,
1.5. Excessof
an inthe ethylene
order between
data,
hydrogen ofthey is
+1 much 0.3derived
[6,11,12].
can and higher,
remove 1.that This
Molero between
theis related
strongly hydrogen
et al. 0.3 to
and
observed
adsorbed the 1.fact
reaction This a thatis
order
reaction
carbonaceous related
ethylene can ordertovary
species isthe the
of factreactant
that ethylene is the react
hydrogen
from
of the
hydrogen catalyst
Regarding between the rate 1–1.25,and
of so
consumption creates
depending freeon surface
of acetylene,the sites.
temperature no that strong for effect is observed fororder ethylene. The
order
foil
between [7]. is close
From
values
for
between ato
of
ethane zero
careful
1 and
1–1.25, as shown
analysis
1.5.
production. Excess
depending by
of numerous
for the
hydrogen
ethane ondata,the production. studies
they
can
temperature derived
remove [12]. forHowever,
strongly theacetylene
acetylene some
hydrogen
adsorbed
hydrogenation
ethylene
hydrogenation reaction
carbonaceous adsorption
over
over
a can
species
Pd
avary
occurs
foil
Pd
[7]. From a
from the
Regardingcatalyst thesurface
rate ofand soby
consumption creates free of acetylene,surface sites. no However, strong
order
foil
between [7].
as indicatedisFrom
close
values byato zero
careful
the
of
Inspection
asanalysis
1small
and shown
negative
1.5.
of theExcess of numerous
reactionthe
value data,
hydrogen
Inspection ofsurface
orders the studies
they reaction
can
of
give derived
the
[12].
remove
valuable order.
reaction that For
stronglytheeffect
insights
orders
some
hydrogen
ethane
is observed
adsorbed
give
into
ethylene
formation,reaction
valuable
the reaction
fororder
adsorption
the
carbonaceous
insights
ethylene.
reaction
mechanism. can occurs
species
into
The
vary
order
the However,
reaction mechanism. Howev
from
order the catalyst
Regarding
is closecareful tothesurface
the
zeroanalysis
rate and
as shown of so the
of consumptioncreatesdata,
by numerous free
they derived
of acetylene, studies sites.
that
[12]. the
no However, hydrogen
strong effect some reaction
is observed
ethylene order can
for ethylene.
adsorption vary between
occurs The values
as
inindicated
between
from ethylene
the values
catalystby
is much 1small
ofsurface and
higher, negative
1.5.between
and Excess
so value
creates hydrogen
0.3 ofand
free the surface reaction
1. can This remove
is
sites. order.
related For
strongly to ethane
the adsorbed
fact formation,
that ethylene the reaction
carbonaceous is the speciesorder
reactant
Regarding this
of by 1to the
needs
and rate to
1.5. asof be consumption
Excess further this
hydrogen validated
needs ofcan acetylene,
to by be
remove deriving
further no
strongly strong
validated
the effect
corresponding
adsorbed bysome is observed
deriving ratethe
carbonaceous for
equation ethylene.
corresponding based The on rate athesequence
equation
catalyst based on a seque
order
as
in
is close
indicated zero
the small shown
negative by numerous
value 0.3of the studies
reaction [12].
is order.
However, For to ethane
ethylene
formation, thespecies
adsorptionreaction from
occurs
order
forethylene
from
order is the
ethane
Regarding
close of
is much
catalyst
production.
to zero
elementarythesurface
as
higher,
rateshown ofand
steps.
between
so
consumption
by creates
numerous
Catalytic
of elementary
and
free
ofstudies
hydrogenation
1.
surface
acetylene, Thissites.
steps. [12].
related
no
Catalytic However, strong
reactions
the fact
effect
some
hydrogenation
of
that
isethylene
unsaturated observed ethylene for is
adsorption
reactions
hydrocarbons
the reactant
ethylene.
of occurs
unsaturated The follow
as
in surface
indicatedisbymuch and
the small so creates
negative free value surface
0.3of sites.
the1.reaction This is order. For to ethane formation, the is reaction order hydrocarbons
often a often follo
forethylene
ethane
Regarding
Inspection production. the
of the
higher,
rate reaction
between
of consumption orders give
and
of acetylene,
valuable
related
no
insights strong into
the fact
effect
the
that
isaccording
reaction observed ethylene
mechanism. for the reactant
ethylene. However, The
asorder
indicated
in
is close
series
by toRegarding
the zero
ofsmall
is much higher,the
asnegative
sequential shown by
hydrogen
series
value
rate of0.3numerous of additions
sequential
the
consumption studies
reaction
and 1. This isofrelated
[12].
according
hydrogen
order. However,
acetylene,For to additions
the
ethane
to theno
some
Horiuti–Polanyi
formation,
strong ethylene the adsorption
to mechanism
the
reaction
effect isisobserved occurs
Horiuti–Polanyi
order [13,15].
for ethylene. This
mechanism [13,15]. T
forethylene
order ethane
Inspection
is close production.
to offurther
zero the asreaction
shown
between
by orders numerous give valuable
studies insights
[12]. However, intoethane the
fact
some reaction
that ethylene
ethylene mechanism.adsorption
the reactant
However, occurs
this
as
infor
ethylene needs
indicated is toby
much
mechanism
The be the
order small
higher, validated
negative
isisreaction
given
close between
tofor mechanism
zero by
value
0.3
acetylene
asgivederiving
andof
shown the
1.
is hydrogenation
given the
reaction
This by numerous corresponding
is for order.
related acetylene to
via For
studiesthe
ethylene rate
fact
hydrogenation
[12]. equation
formation,
that ethylene
toHowever,
ethane based
via the
insome on
reaction
isethylene
the ethylene
Table a sequence
reactant
3. A order
tosingleethane site
adsorptionin Table
for 3. A single site
ethane
Inspection production. of the orders valuable insights into the reaction mechanism.
this
asof needs
indicated
elementary to
isby be the further
steps. small validated
negative
Catalytic by0.3
value
hydrogenation deriving
ofand the the
1.reaction
reactions corresponding
order. ofthe For
unsaturated rate
ethane equation
formation,
hydrocarbons based on
the reactionoften aHowever,
sequence
followordera later on.
forin ethylene
ethane all
production.
Inspection occurs much
surface ofas higher,
species
indicated
the reaction
between
has
by all
been
the
orders surfaceassumed.
small species
negative
give valuable
This
This has
valueisbeen related
assumption of
insights into the assumed. to the
will
reaction fact
be
This that
discussed
order.
reaction
ethylene
assumption
For later
ethane
mechanism.
is
willon. the be
formation, reactant
discussed the reaction
this
of
in needs
elementary
ethylene
series tois be
of sequential much further
steps. higher, validated
Catalytic
hydrogen between by 0.3
hydrogenation
additions deriving
and according the
Thiscorresponding
1.reactions istorelated the of unsaturated to the
Horiuti–Polanyi rate fact equation
hydrocarbons
that mechanism based on
ethylene often
is theaHowever,
sequence
[13,15]. follow
reactant This a
for ethane
Inspection production.
order of theethylene
Hydrogen
in reaction adsorbs orders
is much give
dissociatively
Hydrogen
higher, valuable between adsorbs
on insights
palladium,
0.3 andinto
dissociatively 1. the This reaction
requiring on
is two
related mechanism.
palladium, free
to the neighboring However,
requiring
fact that two
surface
ethylene freeis sites
neighboring
the surface s
this
of
series needs
elementary
of to be
sequential further
steps. hydrogenvalidated
Catalytic by
hydrogenation
additions deriving according the
reactions corresponding
to the of unsaturated
Horiuti–Polanyi rate equation
hydrocarbons
mechanismbased on
often a
[13,15].sequence
follow This a
for ethane
mechanismInspection production.
(step isfurther
given
of the
(1)). for
The acetylene
reactionadsorbed orders
(step hydrogenation
give The
hydrogen
(1)). valuable atom
adsorbedvia insightsethylene
can intoto
hydrogen
react theethane
with reaction
atom in can
adsorbed Table
mechanism. 3.on
react
acetyleneA with single However,
to site
adsorbed form for a acetylene
vinyl to form a vi
this
of needs
elementary
series to be
reactant
of sequential for
steps.hydrogen validated
ethane
Catalytic hydrogenation by
production.
additions deriving according the corresponding
reactions to the of Horiuti–Polanyi rate
unsaturated hydrocarbons equation based
mechanism often a sequence
[13,15]. follow a
mechanism
all Inspection
surface isbegiven
species of the
has for acetylene
reaction
been orders
assumed. hydrogenation
give
This valuable
assumption via ethylene
insights will into
be tothe ethane
discussed reaction in
later Table
mechanism.
on. 3. Aon single However, siteThis for
ofthis
series needs
elementary to
of sequentialsteps.
intermediate further
Catalytic
Inspection in
hydrogenvalidated
step
of hydrogenation
the (2). by
intermediate
This
reaction
additions deriving
intermediate
orders
according reactions
in the
stepgive corresponding
(2).
can of
valuable
toethylene This unsaturated
react
the Horiuti–Polanyi intermediate
with
insights rate
a equation
hydrocarbons
second into can hydrogen
the based
react
reaction
mechanism often
with atom a a sequence
follow
second
mechanism.
[13,15]. to form a hydrogen
adsorbed
However, atom to form adsorb
mechanism
allelementary
this surface
needs to isbe
species given has
further forbeen acetylene
validated assumed. hydrogenation
by This
deriving assumption the via corresponding will to rate
be discussed ethane in
later
equation Table on. based3. Aon single a sequence siteThis for
of
series
mechanismofHydrogen
sequential
ethylene.
this is needs
given
adsorbs
steps. Catalytic
hydrogen
Neurock
to
for be dissociatively
further
acetylene
hydrogenation
additions
and ethylene.
van
validated
hydrogenation
on
according
Santen Neurock palladium,
by reactions
studied
derivingtoand
via the requiring
ethylene
van
ethylene
ofthe unsaturated
Horiuti–Polanyi
Santen two
adsorption
corresponding
to studied
ethane
free
in
neighboring
hydrocarbons
mechanism
on
ethylene
rate
Table a Pd(111)
equation
3. A
often
[13,15].
adsorption
single
surface
surface
based followThis
site
sites
onon
by a sequence
fora aDFT Pd(111)
and surface by DFT a
all
of surface
Hydrogen
elementary species steps. has
adsorbs been
Catalytic assumed.
dissociatively
hydrogenation This assumption
onaccording
palladium, reactions will
requiring
of be
unsaturated discussed
two free later on.
neighboring
hydrocarbons often surface follow sites a
(step
series
mechanism (1)).
of found
is
of The
sequential
given
elementary adsorbed
that for hydrogen
ethylene
acetylene
steps. hydrogen
additions
adsorbs
found
hydrogenation
Catalytic atom
that
at low ethylene
hydrogenation can
coverages via react
to
adsorbs
ethylene the with
as
reactions to adsorbed
Horiuti–Polanyi
a at
di- low species
ethaneof coverages in
unsaturated acetylene
and
Table mechanism
as
at high
3.a Adi-to form
coverage
single
hydrocarbons [13,15].
species site a and
asvinyl
This
for a
often -bonded
at high
follow coverage
a as a -bond
all surface
Hydrogen species has been
adsorbs assumed. This
dissociatively assumption
onaccording
palladium, will be discussed
requiring two freelater on.
neighboring surface sites
(step
series
intermediate (1)).
of The
sequential in adsorbed
step hydrogen
(2). This hydrogen
additions
intermediate atom can canreact reacttowith the with adsorbed
Horiuti–Polanyi
a second hydrogen acetylene
mechanism
atom to
to form
form [13,15]. asite
adsorbed vinyl
This
allmechanism
surface species is
species givenhas
[16]. for
been acetylene
Ethyleneassumed. species
can hydrogenation
This
desorb assumption
[16]. or Ethylene react viawith ethylene
will
can be
atomic
desorb to
discussed ethane
hydrogen
or react laterin
with
to Table
on.form
atomic 3.an A single
ethyl
hydrogen intermediate. tofor form anThisethyl intermediate. T
(step
intermediate
mechanism (1)).series
Hydrogen The
is ingiven
of
adsorbs
step
sequential
adsorbed (2).
for This
acetylene
hydrogen
dissociatively
hydrogen
intermediate
on
atom
hydrogenation
additions
palladium,
can can react via
according
react with
requiring
ethylene with a be second
to
to
the
adsorbed twoHoriuti–Polanyi
hydrogen
ethane
free
in
neighboring
acetylene
Tableatom 3. toAmechanism
to form
form
surface
single asite
adsorbed vinyl [13,15]. This
sites
for
ethylene.
all surface Neurock
species has and been van Santen
assumed. studied
This assumption ethylene adsorption
will discussed on a Pd(111)
later on. surface by DFT and
(step
intermediate (1)).intermediate
Hydrogen mechanism
The adsorbs
in step adsorbed iscan
(2). given
This
react
dissociatively for
hydrogen intermediate
again
intermediate acetylene with
onatom ahydrogenation
palladium,
can
can
second
can react
react reacthydrogen
with
again
requiring with a via
with
second
atom
two a second
ethylene
adsorbed to
free
hydrogen
form hydrogen
toacetylene ethane,
neighboring
ethane atom into which
atom
Table
to surface
formform to
3. has form
A a little
sites
single
vinyl ethane,
interaction
site for which
all has little interact
ethylene.
all
foundsurface that
Hydrogen Neurock
species
ethylene has
adsorbs and been
adsorbsvan Santen
assumed.
atwith
dissociatively low studied
This
coverages
on assumption
palladium,ethylene as aanddi- adsorption
will
requiring species be discussed and
twoon afree
at Pd(111)
later
high on.surface
coverage
neighboring bya adsorbed
assurface -bonded
DFT sites and
(step (1)).
intermediate The
with
surface adsorbed
the
in stepand Pd
species surface
(2). hydrogen
has
ThisSanten and
been
intermediate atom
therefore
the
assumed. Pd can
surface
desorbs
can This react
react assumption
with with
instantaneously
therefore
a secondadsorbed
will desorbs
be (step
hydrogen acetylene
discussed instantaneously
(7)). atom to
later form
on.
to form a
(step vinyl (7)).
ethylene.
found
species
(step that
Hydrogen
(1)).
Neurock
[16]. ethylene
The adsorbs
Ethylene adsorbed adsorbsvan
can at
dissociatively
desorb
hydrogen low studied
orcoverages
reacton with
atom
ethylene
palladium,
can as a di-
atomic
react
adsorption
requiringspecies
hydrogen
with and
adsorbed twoon
to form
afree
at Pd(111)
high coverage
neighboring
an
acetylene ethyl
surface as
intermediate.
to form
by a adsorbed
surface -bonded
DFT sites
a vinyl
and
This
intermediate
ethylene.
found that in
Neurock step (2).
and This
van intermediate
Santen studied can react
ethylene with a
adsorption second hydrogen
on a Pd(111) atom to
surface form by adsorbed
a -bonded
DFT and
species
(step
intermediate [16].ethylene
(1)). The Ethylene
can adsorbed
react
adsorbs
can
again
at low
desorb
hydrogen
with or
a
coverages
react
secondatom with
hydrogencan asatomic a di-hydrogen
react atom
species
with to adsorbed
form
andto at high
form
ethane, the an
acetylene coverage
ethyl
which hasto as
intermediate.
form
little a
interaction vinylThis
intermediate
ethylene.
found in
Neurock andadsorbs
that step (2).
Table
Table This
van Santen intermediate
3.3.atElementary
Elementary studied steps
steps can Table
ethylene for for react the
the with
a3. di-
Elementary
reaction
reaction
adsorption a second
CC2 2H Hsteps
2+
2on hydrogen
+ Hafor 22at C22H
Pd(111) atom
reaction
44 and
and
surfaceCCC to
22H2HH form
44+2by++HH 2
a2DFT2 
adsorbed
CC
-bonded H 22H
2and 6. 46.and C2H4 + H2  C2H6.
species
intermediate
intermediate [16].ethylene
Ethylene
canstep
in react (2). can
again
This desorbwith
low
intermediate or coverages
react with
adesorbs
second hydrogen
can
asatomic
react atom
with hydrogenspecies
a to secondformto
and form
ethane,
hydrogen
high an which
coverage
ethyl
atom has toas
as
intermediate.
little
form interaction
adsorbed This
withthat
ethylene.
found the ethylene
Pd
Neurocksurface andand
adsorbs vantherefore
at Santen
low studied
coverages instantaneously
ethylene
as a di- adsorption
species (step and (7)).
onat a Pd(111)
high coverage surface a by-bonded
DFT and
species [16]. Ethylene can desorb aor react with atomic hydrogen toethane,
form an ethyl σintermediate.
 surface This
intermediate
with the
ethylene.
found that PdNeurock can react
surface
ethylene and
and again
adsorbs therefore
van with
Santen
at low
second
desorbs N◦N°
studied
coverages
hydrogen
instantaneously
ethylene as a di-
atom
Elementary
Elementary
adsorptionspecies
to(stepform
N° Step
Step
(7)).
on at a high
Pd(111)which
Elementary has little
Step
asby DFT and
interaction
a -bonded
species
intermediate[16]. Ethylene
can react can desorb
again with orareact second with hydrogen atomic hydrogen
atom to form toand form
ethane, an whichethylcoverage intermediate.
has little interaction This
with the
found Pd surfaceTable 3.and therefore desorbs 1 instantaneously C2H +++H
22 species 2*(step 1C
2  2H*
(7)).
2H* Hcoverage
2+ 2
+H2*  2H*
22 C2H as6. a -bonded 2
speciesthat
intermediate [16].ethylene
Ethylene adsorbs
Elementary
can desorb at low stepsor coverages
for
react1 the with reaction asatomica di- Hhydrogen
2 to 2* and H4form
2to at high
and Can 2H4ethyl
hasintermediate. This
with the Pdcan surface reactand again with a second
therefore desorbs hydrogen
2 instantaneously atom
C H +
form ethane,
(step
*  2 C (7)).
H *
which
C H 
little interaction
+ H2 1intermediate.
1 + * C H *
species
intermediate
Table 3. Elementary
[16]. Ethylene
can react can again desorb
with
steps for2 thewith
aorsecond
react reaction
hydrogen atomic CC2H 22H
atom
2 + 22+
hydrogen H*2 C22H
to form
2 2*and Can
toethane,
42 form 2H4 ethyl
2
which has
2 C2H6. 2 2
little interaction This1
with the Pd surface Tableand therefore N° desorbs instantaneously
Elementary Step (step  (7)).  
to  little
3. Elementary steps for3 the reaction
3 hydrogen C C
C22HatomH 2 H *
22* + H*
2 + + H
H* 2 C H
3C22Hethane,
2 4 and
*
33* + C+ * C H
* 2Hwhich
2 +
2* + 1
4 H H*has
2 1 C H
C2H3*interaction
2 6. +* 1
intermediate can react again with a second form
with the Pd surface Table 3.and therefore
Elementary N° 1 desorbs
steps for4 theinstantaneously
Elementary
reaction
H2 +CC 2*22C H2H 2Step
3**2H* ++ H* H(step2  C2
(7)).and
2H44 * +2* C2H4 + H2  1 C2H6.
4 H + H*  4C H * + C
* H * + 1H*  C H * + * 1
+ * 2C
with the PdTable surface and therefore 3 2 4 2 3 2 4
3. Elementary N°
steps 12 desorbs
for the 5 reaction instantaneously
Elementary
C H 2H 2 2+ + 2**2H
C C2 2+2H*
CHStep
H *2 
24H2* 2 4
(stepC 2H(7)). 4 and
1 2H4 + H2  1 C2H6.
Table 3. ElementaryN° 5 Elementary C 2HStep
*24++* H*  C52H4 +and
2  C 2H4 *  * CC
*+ 2H4*1  C2H4 + * 1
12steps for6 the
3 C 2HC reaction
H 22H 2 + 2*
* +2 +H*
C* 2C
H

2H 4C2H*
C2+22+H H
H 23** + * 2 5 2 11 2H4 + H2  1 C2H6.
Table 3. Elementary N°1steps for 7 Elementary
6
the reaction CC CH
5C
H Step
H ** + H*
H
H* 
 6
CC HH  *
and
+ +2* C
* C H H * ++ H1H* 1  C C H H * + * 1
23 C 22H C2H 2H 2 2++2* 2
* 2 
2 4 2H* 22H 23*
2 2 6 2
22 4 5
1 2 2 44 2 2 2 6. 5

1N° 4 C7 H H23**+++2*H*
Elementary H*
C  H2H*
C
* CStep
+ 2H HH* 4** ++ **
 7C H 2 + 112* C H * + 1H*  C H + 2* 1
23 C C22*H+2 H* + * 2C 5 C22H H32** + * 2 6 1 2 5 2 6
N° 45
1 C22H H 32*
Elementary
C H H +4+*H* 2*  
 C C 2H
2Step
2H* H 4 4+ * *+ * 11
2 1
2 C2H 2H 2 + * 
2 C2CH2H 2* 3* + * 11
Hydrogen
Even thoughadsorbs the13425reaction Even C
Cmechanism
dissociatively2H
C22though
C
23*
H2+H
* 2++4*+H*
H H* 
2**on
the is
C C 2H
palladium,
reaction
2H*still
H 4 4+* *+ *mechanism
rather requiring
simple, 2111 the istwostill free
derivation
rather neighboring
simple,
of the corresponding thesurface derivation sitesof the correspond
3 46 *H* +2 +H* 2C H
C2C H *C 24H  C CH 232H * 25*** + *
+ 11
(step (1)). The adsorbed 5 hydrogen 2C H 3H *
atom + * H* 
can  C
2C H
react 2H 4* *+ *
+ with adsorbed 1
1 acetylene to form a vinyl intermediate
rate-equation requires23rate-equation 6severalC Cassumptions.
2H C 2 425*
*H*requires
+++2 H*
4
+H* * 2C
2
CC We
several
2H 4
H32+56assume
** +*++2***assumptions.that 111 the adsorption We assumetake thatplace the adsorption
according to take place according
4 57 C2H C 232H
C*H22+H H* 4*H*
H*
  C CC 2H H
2242H
4* + *is 11 1
in step
the Langmuir (2). This isotherm 3 6
intermediate
the
7 [17]. Langmuir
TheC
C
C H
2can
H
2H23*next45* * +
react
isotherm
+
+ H* assumption
H* 
with C H
2[17].
H a 56*second
+ +The
2**with next hydrogen
respect1assumption
1 to atom
the to form
rate-determining
is with respectadsorbed to step
the ethylene.
rate-determining
for the step for
5 46mechanism C 2
C222H H4is 4* * ++still H*
 Crather 2HC C422+H 2
H*34** ++ ** 11
1
Even though
Neurock the
and reaction
van Santen 7 studied C
C HH ** +
ethylene H*
H* 
 C
C 2H H
adsorption 5*++2*
simple, * the
on a1
1derivation
Pd(111) of
surface the corresponding
by DFT and found that
formation of ethylene45formation and ethane. C2H 2 of23H5
*Since+4*H* CC
for and
both
2
2H
6
4+* ethane.
steps
*+ * the Since reaction
11 for both order steps in hydrogen
the reaction was order
found in to
hydrogen was found
Evenethylenethough the reaction 6 7mechanism C2C H2H 4C* is5+ H*+still  C2C
rather 2H H 54*simple,
6+ +* 2*of the 1 derivation of the
rate-equation be larger requires adsorbs
than several
1, the 5
assumptions.
at additions
low be coverages
larger of
than
C the H
* as We 1, H*athe
second
*
assume
di-σ additions
C
2H
species
hydrogen
H +
that
*
theatom
and the atsecond
1
1high
adsorption to the coveragetake
hydrogen
vinyl and ascorresponding
place aethyl
atom according
π-bonded to
intermediates
the to and
species
vinyl [16].
areethyl intermediates
Even though the reaction 6
mechanism 2CH25H *is
2 4+* H* + H*
4
still  
rather C
2
H26Hsimple,
4 5* 2*+ *thethe 1
1 derivation of the corresponding
rate-equation
the Langmuir Ethylene requires
isotherm can [17]. 7The
several
desorb or nextCassumption
assumptions.
react with We
atomic assumeC2with
ishydrogen
+that respect to formadsorption
to the an take
rate-determining
ethyl place
intermediate. according
step This for to
the
intermediate
assumed
Even though
rate-equation requires to be
the reaction rate-determining
several 67assumed
mechanism
assumptions. C to
C22H (steps
His be
45* *We ++ H*
still H* assume
rate-determining
(4) and
with
rather C
C22H (7),56*++2*
Hsimple,
that respectively).
*thethe (steps 11 (4)
derivation
adsorption and
All other
(7),
take respectively).
of place steps
the corresponding are
according assumed All to otherto be
steps
in are assumed to b
the Langmuir
formation canof isotherm
ethylene
react again [17].
and with The
ethane.a next
second Since assumption
for
hydrogen both is
steps
atom the
to respect
form reaction to the
ethane, order rate-determining
which in hydrogen
has little was stepfound
interaction for the to
with the Pd
the
Even though
rate-equation
Langmuir
the reaction
requires
isotherm several
[17].ethane.
mechanism
The 7 next assumption
assumptions. C2is H5still *We + H* rather with
assume
is Csimple,
2Hthat 6 + 2*
respect thetheadsorption
derivation
to the 1 rate-determining of the
take placecorrespondingaccording
step for the to
formation
be largerEven surface of ethylene
than
though 1, thetheseveral
and and
additions
reaction
therefore of
mechanismthe
desorbs Since second forisboth
instantaneously hydrogen
still steps
rather the
atomsimple,
(step reaction
to (7)).the
the vinyl order
derivation in hydrogen
and ethyl
of the was
intermediates
corresponding found to
are
rate-equation
the Langmuir
formation requires
isotherm
of ethylene [17].
and assumptions.
The
ethane. next Since assumption We
forisboth assume is with
steps that
the respectthe
reaction adsorption
tovinylthe
order take
rate-determining
in hydrogen place according
was step found for the to to
be larger
assumed Even than
though
to isotherm1,
berequires the
the additions
reaction
rate-determining of
mechanismthe
(steps second(4) and hydrogen
still
We(7), rather
respectively).atom simple, to the
the derivation and ethyl
of theintermediates
corresponding are
therate-equation
Langmuir
formation
be larger than of ethyleneEven though
1,rate-determining
the additions
several
[17].
and The theassumptions.
ethane. next
of
reaction
the assumption
Since
second
mechanism
for both
hydrogen isassume
with
steps is the still that
respect
atom
the
rather
reaction
to toAll
the
adsorption
simple,
the other
order
vinyl
steps
the
rate-determining
andin take
hydrogen
ethyl
areplace
derivation assumed according
step
was
intermediates
of found
the
for tothe beto
to
in
corresponding
assumed
rate-equation
the Langmuir to berequires
isotherm
rate-equation several
[17].
requires The (steps
assumptions.
next
several (4)assumptions.
assumption and We (7), assumerespectively).
is with We that
respect
assume the All
to other
adsorption
the
that steps take
rate-determining
the adsorption are placeassumed according
take step to
place for bearethein
to
according to
formation
be largerof thanethylene 1, the and additions ethane. Since
of(stepsthe second for both hydrogen steps the atom reaction to the order
vinyl inand hydrogen
ethyl was found to
assumed
the Langmuir to beisotherm
rate-determining [17]. The next (4) and
assumption (7), is respectively).
with respect All
to other
the steps
rate-determining areintermediates
assumed step tofor bethearein
beformation
larger than
assumed to
of1,ethylene
the beLangmuir
the additions
rate-determining
and ethane.
isotherm of the (steps
Since
[17].
second The forhydrogen
(4) and next bothassumption steps atom
(7), respectively).
the to reaction
isthe with vinyl
All
order
respect
other andstepsinethyl
tohydrogen
the are
was found to
rate-determining
intermediates
assumed to are be in step for the
formation
be larger of ethylene
than 1, the and ethane.
additions of the Since
second for both hydrogen steps atom the reaction to the orderand
vinyl in hydrogen
ethyl was foundare
intermediates to
assumed to be rate-determining (steps (4) and (7), respectively). All other steps are assumed to be in
be larger than
assumed to be 1, the additions of(steps
rate-determining the second (4) and hydrogen (7), respectively). atom to the Allvinyl otherand steps ethyl areintermediates
assumed to beare in
assumed to be rate-determining (steps (4) and (7), respectively). All other steps are assumed to be in
Catalysts 2019, 9, 180 4 of 13

formation of ethylene and ethane. Since for both steps the reaction order in hydrogen was found to
be larger than 1, the additions of the second hydrogen atom to the vinyl and ethyl intermediates are
assumed to be rate-determining (steps (4) and (7), respectively). All other steps are assumed to be in
quasi-equilibrium. To reduce the number of parameters in the rate equation only the most abundant
reaction intermediates are kept in the site balance. The full site balance is given as:

θ∗ + θ H + θC2 H2 + θC2 H3 + θC2 H4 + θC2 H5 = 1

Here, we assume that the coverages of vinyl and ethyl intermediates are much smaller than those
of adsorbed acetylene and ethylene and thus can be left out of the site balance. A combined DFT
Monte-Carlo study for acetylene hydrogenation over Pd(111) at a hydrogen to acetylene ratio of 1,
showed that this is indeed the case [13]. This same study indicates that the hydrogen coverage is not
negligible and that it is larger than the ethylene coverage. Here, we take into account the ethylene
coverage, because a negative reaction order in ethylene was observed. The last model assumption
states that the rate-determining steps, (4) and (7), are irreversible (or one-way) under the given
reaction conditions.
The rates for the two rate-determining steps can be written as:

r4 = k4 θC2 H3 θ H = k4 K1 K2 K3 PC2 H2 PH2 θ∗2

K1
r7 = k7 θC2 H5 θ H = k7 K6 PC2 H2 PH2 θ∗2
K5
and the site balance is given by:
1 = θ∗ + θ H + θC2 H2 + θC2 H4

or:
1
θ∗ =  PC2 H4 p 
1 + K2 PC2 H2 + K5 + K1 PH2

By introducing the number of palladium surface atoms per catalyst mass, NS (mol Pds /kgcat ),
and attributing all temperature effects to the change of the rate constant in the rate-determining steps,
thus assuming that the adsorption equilibrium constants do not change between 51 and 62 ◦ C, the
following rate equations are obtained for the consumption of acetylene and the production of ethane,
respectively:  
E4
NS k04 exp − RT K1 K2 PC2 H2 PH2
− rC2 H2 = 
PC H 2
p 
1+ K1 PH2 + K2 PC2 H2 + K25 4
  
E7 K1
NS k07 exp − RT K5 PC2 H4 PH2
rC2 H6 = 
PC H 2
p 
1 + K1 PH2 + K2 PC2 H2 + K25 4

Notice that k4 and k7 in the above equation are actually a combination of k4 *K3 and k7 *K6 ,
respectively. Table 4 gives the correspondence between the reaction orders of the rate equations and
the surface coverages as well as the range of reaction orders that are covered by the model.

Table 4. Reaction orders corresponding to the derived rate-equations.

rC2H2 rC2H6
Reaction Order
C2 H2 H2 C2 H4 C2 H2 H2 C2 H4
dependence on coverage 1−2θC2H2 1−θH2 −2θC2H4 −2θC2H2 1−θH2 1−2θC2H4
Min–max (−1)–1 0–1 (−2)–0 (−2)–0 0–1 (−1)–1
Catalysts 2019, 9, 180 5 of 13

The reaction order with respect to acetylene is smaller for the ethane production than for the
acetylene consumption, whereas the reaction order with respect to ethylene is larger for the ethane
production than for the acetylene consumption, in agreement with the experimental results. Taking
the experimental reaction orders from Table 3, the mean coverage averaged over all tested reaction
conditions of acetylene, hydrogen and ethylene can be estimated as θC2H2 = 0.65–0.95, θH2 ≈ 0 and
θC2H4 = 0.06–0.15.
In order to estimate the 7 parameters in the two rate equations, a multi-response regression
analysis of the two data sets at 51 and 62 ◦ C was carried out simultaneously. Initial results showed that
all parameters were strongly correlated and no accurate estimates could be determined. Therefore, the
hydrogen equilibrium constant was set at a fixed value, calculated from literature data. The following
expression is used to calculate the adsorption equilibrium constant:

σs AS 1  
Ki = √ Ed
Pa−1
2πMw RT 1013 e(− RT )

where σs is the sticking coefficient, AS the surface area of Pd (1.26 104 m2 /mol), Mw the molecular
weight (kg/mol) and Ed the desorption activation energy (J/mol). A typical value for the
pre-exponential factor for desorption of 1013 s−1 was assumed. Assuming a sticking coefficient
for hydrogen adsorption of 0.16 (0.1–0.2 [18] and 0.17 [19]) and a desorption energy of 69 kJ/mol [20],
a value of 611 Pa−1 was estimated for K1 . Fixing the adsorption equilibrium constant for hydrogen
forces the model to account for the hydrogen coverage, else due to the hydrogen reaction order ≥1 the
hydrogen coverage would be close to zero. Further regression analysis still showed an unacceptable
correlation between the parameters. To get an accurate estimate of the adsorption equilibrium constant
for acetylene the adsorption equilibrium constant for ethylene had to be set at a fixed value. Although
it is not evident from the two rate equations, the correlation between these two equilibrium constants
(K2 and K5 ) can be revealed by expressing the ethane selectivity as:

rC2 H6 rC H k PC H 1
SC2 H6 = ≈ 2 6 = 7 2 4
rC2 H2 + rC2 H6 rC2 H2 k4 PC2 H2 K2 K5

Apparently, the rate constants k7 and k4 can be decoupled by fitting the conversion and ethane
production but not the term K2 *K5 . However, the absolute values of k7 and k4 will depend on the
values of K2 and K5 .
As stated above, ethylene is adsorbed at low coverages as a di-σ species or at high coverage as
a π-bonded species with adsorption enthalpies of −60 and −30 kJ/mol, respectively [16]. A TPD
study gave a value of the adsorption enthalpy of −59 kJ/mol [21]. This value was used to estimate the
equilibrium constant for ethylene at a value of 0.14 Pa−1 . Table 5 reports the values of the parameter
estimates with their 95% confidence intervals from the regression analysis of all data. The parameters
can be accurately estimated with 95% confidence intervals at the 10% level for those related the
acetylene conversion and 20% for the ethane production, similar as the relative standard deviations
on the repeated runs (Table 1). No strong parameter correlation was observed; the highest value
of 0.85 was between k0 4 and E4 . The value of the equilibrium adsorption constant for acetylene is
approximately 3 orders of magnitude higher than that of ethylene. This corresponds to an enthalpy
of adsorption for acetylene of (−80)–(−90) kJ/mol. Vattuone et al. [22] measured differential heat of
adsorptions of acetylene over a single crystal of Pd(100) by calorimetry from 110–40 kJ/mol, decreasing
with increasing acetylene coverage.
Catalysts 2019, 9, 180 6 of 13

Table 5. Parameter estimates with their 95% confidence intervals.

Parameter Estimated Value

K1(Pa−1 ) 13 (fixed)
K2 (Pa−1 ) 107 ± 7
k0 4 (mol/mol Pds /s) 1.4 ± 0.1 × 108
K5 (Pa) 7.4 (fixed)
k0 7 (mol/mol Pds /s) 3.6 ± 0.6 × 109
E4 (kJ/mol) 48.5 ± 4.2
E7 (kJ/mol) 54.8 ± 11
NS (mol/kg) 2 × 10−3 (fixed)

An adequate fit of the data was obtained, as shown in Figures 1–6, organized per inlet flow of
acetylene, ethane and hydrogen for both the acetylene conversion and ethane production. Although
the model corresponds to a hydrogen reaction order of approximately 1, both the acetylene conversion
and ethane production are well fitted by the model, especially at 51 ◦ C. The power law model gave a
significantly larger value for the hydrogen reaction order (~1.45 at 51 ◦ C, Table 2). The cause of this
discrepancy between the two models is not clear. The surface coverages as calculated by the model are
in the range of θC2H2 = 0.62–0.95, θH2 = 0.002–0.01 and θC2H4 = 0.04–0.36.
This is in good agreement with the surface coverages as calculated from the reaction orders.
The apparent activation energy for the conversion of acetylene compares well with the value of
40 kJ/mol reported in the literature for acetylene hydrogenation over a Pd foil [7].
The proposed reaction mechanism based on a single site can adequately represent the experimental
data, as shown in Figures 1–6. Neurock and coll. [13] could describe independent experimental data
correctly by the same reaction mechanism as the one proposed in this study using also a single site.
Bos et al. [6] could describe their experimental data by very similar rate equations as used here, in the
absence of carbon monoxide. However, the addition of carbon monoxide to the feed resulted in a
change of the ethane selectivity, which cannot be explained by the above model. As mentioned in the
introduction, it could well be that the second site is related to the presence of carbon monoxide on the
surface, which is known to have a strong electronic effect and can cause surface reconstruction.
Numerous other studies [2–4,8,9] and notably the model proposed by Borodziński and
Cybulski [4] are based on two distinct active sites. We therefore performed a regression analysis
of the model proposed by Borodziński and Cybulski to our data set (we used the equations given
in the Appendix A of their article, which differ from the text) [4]. The regression analysis showed
that the parameters associated with the second site were not statistically significant and the model
was reduced to a single site model. The arguments of Borodziński and Cybulski [4] for a two-site
model was that they observed a lack of the effect of the partial pressure of ethylene on rC2H2 /PH2 ,
indicating that the coverage of active sites by ethylene is negligible, while they observed an effect
of the partial pressure of ethylene on rC2H4 /PH2 . The latter effect is also observed in this study and
corresponds to the data in Figure 4. The rate of ethane production increases with the partial pressure
of ethylene (the partial pressure of ethylene is proportional to the molar flow of ethylene in Figure 4,
where the partial pressure of acetylene and the partial pressure of hydrogen are constant). Contrary to
Borodziński and Cybulski, we do observe an effect of the partial pressure of ethylene on rC2H2 /PH2 .
This is demonstrated in Figure 7 where we trace both the data of Borodziński and Cybulski [4] and
our data for rC2H2 /PH2 as a function of the partial pressure of ethylene. Despite the rather different
conditions of both studies, the rC2H2 /PH2 values are very similar. However, whereas rC2H2 /PH2 is
independent of the ethylene partial pressure in the case of the data of Borodziński and Cybulski, in our
case, rC2H2 /PH2 decreases with increasing ethylene partial pressure. A single site mechanism is thus
validated for the conditions used in this study, or at least if two sites are present on the catalyst, the
adsorption behavior of ethylene and acetylene on both sites is not different enough to be distinguished
from the experiments under these conditions. Borodziński and Cybulski [4] attributed the different
active sites on palladium to the deposit of carbonaceous species, creating pockets of different sizes
Catalysts 2019, 9, 180 7 of 13

that induce size dependent reactivity. In our study, the amount of carbonaceous species might be
Catalysts 2019, 9, x FOR PEER REVIEW
rather low, due to the short time on stream of the catalyst and the much higher stoichiometric7 ratio
of 13

of hydrogen to acetylene. This is also consistent with the reaction order of hydrogen greater than 1,
Catalysts was
which 2019, explained byREVIEW
9, x FOR PEER Molero et al. [7] by excess hydrogen that removes adsorbed carbonaceous
7 of 13
species from the catalyst surface and creates free palladium sites.

Figure 1. Evolution of acetylene conversion as a function of the acetylene inlet molar flow. Circles:
data at 62 °C, squares: data at 51 °C.
Figure 1. Evolution of acetylene conversion as a function of the acetylene inlet molar flow. Circles:
data at 1. ◦ C, squares: data at 51 ◦ C.
62Evolution
Figure of acetylene conversion as a function of the acetylene inlet molar flow. Circles:
data at 62 °C, squares: data at 51 °C.

Figure 2. Ethane outlet molar flow as a function of the acetylene inlet molar flow. Circles: data at 62 ◦ C,
squares: data at 51 ◦ C.
Figure 2. Ethane outlet molar flow as a function of the acetylene inlet molar flow. Circles: data at 62
°C, squares: data at 51 °C.

Figure 2. Ethane outlet molar flow as a function of the acetylene inlet molar flow. Circles: data at 62
°C, squares: data at 51 °C.
 Catalysts 2019, 9, x FOR PEER REVIEW 8 of 13

Catalysts
Catalysts 2019,
2019, 9, x FOR PEER REVIEW
9, 180 8 of813
of 13

Figure 3. Evolution of acetylene conversion as a function of the ethylene inlet molar flow. Circles:
data 3.
Figure at Evolution
62 °C, squares: data at 51
of acetylene °C.
conversion as a function of the ethylene inlet molar flow. Circles: data
at 62 ◦ C, squares: data at 51 ◦ C.
Figure 3. Evolution of acetylene conversion as a function of the ethylene inlet molar flow. Circles:
data at 62 °C, squares: data at 51 °C.

Catalysts
Figure 2019, 9, x FOR outlet
4. Ethane PEER REVIEW
molar flow as a function of the ethylene inlet molar flow. Circles: data at 629◦of
C, 13
squares: data at 51 ◦ C.
Figure 4. Ethane outlet molar flow as a function of the ethylene inlet molar flow. Circles: data at 62
°C, squares: data at 51 °C.

Figure 4. Ethane outlet molar flow as a function of the ethylene inlet molar flow. Circles: data at 62
°C, squares: data at 51 °C.

Figure 5. Evolution of acetylene conversion as a function of the hydrogen inlet molar flow. Circles:
data at 625.◦ C,
Figure squares:ofdata
Evolution at 51 ◦conversion
acetylene C. as a function of the hydrogen inlet molar flow. Circles:
data at 62 °C, squares: data at 51 °C.
 Figure 5. Evolution of acetylene conversion as a function of the hydrogen inlet molar flow. Circles:
data
Catalysts at 62
2019, °C, squares: data at 51 °C.
9, 180 9 of 13

Figure 6. Ethane outlet molar flow as a function of the hydrogen inlet molar flow. Circles: data at 62 ◦ C,
squares:
Catalysts 9,data
2019,6. x FOR 51 ◦ C.REVIEW
at PEER 10 of 13
Figure Ethane outlet molar flow as a function of the hydrogen inlet molar flow. Circles: data at 62
°C, squares: data at 51 °C.
0.35
RC2H2/PH2, mol/mol Pds /s /kPa

0.30

0.25

0.20
0 10 20 30 40 50 60 70 80 90
PC2H4, kPa

Figure 7.
Figure 7. Plots
Plots ofof rrC2H2
C2H2 /P/P
H2 vs.vs.
H2 ethylene partial
ethylene pressure.
partial Open
pressure. symbols:
Open datadata
symbols: fromfrom
Borodziński and
Borodziński
Cybulski
and [4]: T[4]:
Cybulski = 70 70P◦C2H2
T =°C, C, P=C2H2
0.02=kPa,
0.02PkPa,
H2 = 0.64
PH2 kPa.
= 0.64Closed symbols:
kPa. Closed data from
symbols: datathis study:
from T = 62
this study:
°C,
T = P62 ◦ C,
C2H2 = 0.95
PC2H2kPa,=P H2 = kPa,
0.95 5.5 kPa.
PH2The dotted
= 5.5 kPa.horizontal
The dottedlinehorizontal
indicates the
lineextrapolated
indicates theaverage values
extrapolated
of rC2H2/Pvalues
average H2 for the
of rdata
C2H2 /Pfrom
H2 Borodziński and Cybulski
for the data from [4]. and Cybulski [4].
Borodziński

3.
3. Materials
Materials and
and Methods
Methods
3.1. Experimental set-up and testing
3.1. Experimental set-up and testing
Kinetic experiments for acetylene hydrogenation were carried out in an integral fixed bed reactor
Kinetic experiments for acetylene hydrogenation were carried out in an integral fixed bed
over 0.05 wt. % Pd/α-Al2 O3 catalysts under typical tail-end conditions. During the experiment, 0.1 g of
reactor over 0.05 wt. % Pd/α-Al2O3 catalysts under typical tail-end conditions. During the experiment,
catalyst sieved between 100 and 200 µm was used, diluted with 0.5 g of the α-Al2 O3 support, crushed
0.1 g of catalyst sieved between 100 and 200 µm was used, diluted with 0.5 g of the α-Al2O3 support,
and sieved identically, to improve the isothermicity of the catalytic bed. The fixed-bed reactor consisted
crushed and sieved identically, to improve the isothermicity of the catalytic bed. The fixed-bed
of a quartz tube with an inner diameter of 4 mm, inserted in a cylindrical oven. A thermocouple
reactor consisted of a quartz tube with an inner diameter of 4 mm, inserted in a cylindrical oven. A
was inserted into the catalyst bed. The reaction was carried out at 51 and 62 ◦ C. A flow consisting of
thermocouple was inserted into the catalyst bed. The reaction was carried out at 51 and 62 °C. A flow
different ratios of acetylene, ethylene, hydrogen, and argon, using mass flow controllers, at a total flow
consisting of different ratios of acetylene, ethylene, hydrogen, and argon, using mass flow controllers,
at a total flow rate of 200 mL/min was used and the reactor was operated at 1.26 bar. The experiment
at standard conditions was performed regularly to check the stability of the catalyst and the data
repeatability. The reactor was loaded twice with a fresh catalyst sample and the experiments were
conducted twice. Before the experiments the catalyst was reduced under a flow of 100 mL/min of 50%
Catalysts 2019, 9, 180 10 of 13

rate of 200 mL/min was used and the reactor was operated at 1.26 bar. The experiment at standard
conditions was performed regularly to check the stability of the catalyst and the data repeatability.
The reactor was loaded twice with a fresh catalyst sample and the experiments were conducted twice.
Before the experiments the catalyst was reduced under a flow of 100 mL/min of 50% hydrogen in argon
at 150 ◦ C for 2 h. The catalyst activity and selectivity were found to be stable during the kinetic runs.
Online analysis was done by passing the outlet gas flow through a small volume infrared gas cell
connected to a FTIR spectrometer. Quantitative FTIR analysis of acetylene, ethylene and ethane was
carried out. No C4 products were observed. The carbon balance was closed within 5%. Experimental
conditions are given in Table 6. By using appropriate criteria, the kinetic measurements were shown to
be free from heat and mass transfer limitations [23]. This can be easily verified using the tool developed
by Eurokin [24]. The maximum observed rate of acetylene consumption of 9 mmol/kgcat /s was used
to check the criteria given in Table 7. As shown in Table 7 all criteria were met.

Table 6. Experimental conditions.

Variable Values
T (◦ C) 51, 62
FC2 H2 (µmol/s) 0.7–3
FH2 (µmol/s) 1.6–10
FC2 H4 (µmol/s) 29–105
FAr (µmol/s) 34–115
P (bar) 1.26
Wcat (g) 0.1
Ftot (µmol/s) 149

Table 7. Criteria to assess the conditions for the absence of mass and heat transfer limitations.

Physical Phenomenon Criteria

plug flow (axial) h/dp = 193 > 6
plug flow (radial) dR /dp = 40 > 10
degree of dilution (vol./vol.) 0.89 < 0.97
external mass transfer (Carberry number) 3.3 × 10−4 < 0.05
internal mass transfer (Weisz-Prater) 1.7 × 10−2 < 0.33
external heat transfer (film) 0.14 K < 1.1 K
external heat transfer (radial) 0.17 K < 1.1 K
internal heat transfer 3 × 10−3 K < 1.1 K

3.2. Catalyst
0.05 wt. % Pd supported on α-alumina was used as a catalyst. It was prepared by impregnation
of the alumina by an aqueous palladium nitrate solution. The material was then dried at 120 ◦ C
under ambient air and calcined at 425 ◦ C for 2 h. The detailed protocol has been previously described
together with extensive XRD and HRTEM characterization [25,26]. The alumina support has a porous
volume of 0.54 mL/g and a BET surface area of 10 m2 /g. Electron Transmission Microscopy analysis
showed a mean particle diameter of 2.4 ± 0.7 nm, corresponding to a dispersion of ca. 40%. From this
and the wt. % of Pd the number of surface palladium atoms was calculated as NS = 2 × 10−3 mol/kg.
The catalyst was sieved between 100 and 200 µm to improve the heat transfer during the kinetic
experiments. Runs under standard conditions using the original catalyst spheres in a single pellet
reactor configuration showed similar performance as the crushed sample.

3.3. Modeling
An integral reactor operation was used and the rate equations have been integrated numerically
using the ODEPACK library [27]. A one-dimensional homogeneous reactor model has been used,
in agreement with the absence of mass and heat transfer limitations. A non-linear least-square
Catalysts 2019, 9, 180 11 of 13

multi-response regression analysis has been performed by a Levenberg–Marquardt minimization

algorithm [28,29]. The fractional acetylene conversion and the molar exit flow of ethane (µmol/s)
have been used for the objective function. No weighing factor has been applied. After regression
analysis several statistical tests were performed, including the t-test, the 95% confidence intervals of
the parameter estimates, the F-value, and binary correlation coefficients.

4. Conclusions
The kinetics of the selective hydrogenation of acetylene over a 0.05 wt. % Pd/α-Al2 O3 catalyst
was studied under intrinsic kinetic conditions. The operating conditions were chosen according to
the tail-end process. Analysis of the experimental reaction orders gave good insight into the reaction
mechanism. It allowed us to estimate the mean surface coverages of hydrogen, acetylene, and ethylene.
The proposed reaction mechanism consists of a series of sequential hydrogen additions according to
the Horiuti–Polanyi mechanism. The derived rate equations are based on the addition of the second
hydrogen atom as rate-determining step for both acetylene and ethylene hydrogenation. Accurate
parameter estimation was only possible after fixing the values of the equilibrium adsorption constant of
ethylene. The relatively simple Langmuir–Hinshelwood-type rate-equations describe the experimental
data adequately. It is based on physically meaningful parameters. The reaction mechanism involves
only one active site, which was carefully verified.

Author Contributions: Conceptualization, J.-M.S., Y.S. and A.C.; methodology, J.-M.S., Y.S.; software, Y.S.;
validation, Y.S., J.-M.S.; formal analysis, C.U., Y.S.; investigation, C.U.; resources, A.C.; data curation, Y.S.;
writing—original draft preparation, C.U.; writing—review and editing, J.-M.S., Y.S. and A.C.; visualization, C.U.;
supervision, J.-M.S., Y.S. and A.C.; project administration, J.-M.S.; funding acquisition, J.-M.S., A.C.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

Appendix A

Nomenclature
AS Surface area of Pd 1.26 × 104 m2 /mol
dp Catalyst particle diameter m
dR Reactor diameter m
E Activation energy kJ/mol
F Molar flowrate µmol s−1
h Bed height m
k0 Pre-exponential factor (mol/mol Pds /s) or s−1
k Rate constant (mol/mol Pds /s)
K Adsorption equilibrium constant Pa−1
Mw Molecular weight kg/mol
NS Number of surface Pd atoms mol Pds /kg
P (Partial) pressure bar, Pa or kPa
R Gas constant J/mol/K
ri or Ri Reaction rate for species i or step i mol/kg/s
SC2H6 Selectivity of ethane -
T Temperature ◦ C, K

Wcat Catalyst mass g

X Conversion %mol
Catalysts 2019, 9, 180 12 of 13

Greek letters and symbols

* Active site
αi Acetylene reaction order for reaction i
βi Hydrogen reaction order for reaction i
γi Ethylene reaction order for reaction i
σ Stoichiometric number
σs Sticking coefficient
θi Fractional surface coverage of species i

References
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cracking. Stud. Surf. Catal. 1986, 27, 613–666.
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Catalysts. Part 1. Effect of Changes to the Catalyst During Reaction. Catal. Rev. 2006, 48, 91–144. [CrossRef]
3. Bos, A.N.R.; Westerterp, K.R. Mechanism and kinetics of the selective hydrogenation of ethyne and ethane.
Chem. Eng. Process. 1993, 32, 1–7. [CrossRef]
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