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Applied Catalysis A: General 483 (2014) 7684

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Applied Catalysis A: General


journal homepage: www.elsevier.com/locate/apcata

Causes of deactivation of bifunctional catalysts made up of


CuO-ZnO-Al2 O3 and desilicated HZSM-5 zeolite
in DME steam reforming
a, , Lide Oar-Arteta a , Miren J. Azkoiti b ,
Ana G. Gayubo a , Jorge Vicente a , Javier Erena
a
a
Martin Olazar , Javier Bilbao
a
b

Departamento de Ingeniera Qumica, Universidad del Pas Vasco UPV/EHU, Apartado 644, 48080 Bilbao, Spain
Departamento de Ingeniera Qumica y Medio Ambiente, Universidad del Pas Vasco UPV/EHU, Paseo Rafael Moreno Pitxitxi 3, 48013 Bilbao, Spain

a r t i c l e

i n f o

Article history:
Received 11 February 2014
Received in revised form 18 June 2014
Accepted 26 June 2014
Available online 6 July 2014
Keywords:
DME
Steam reforming
Hydrogen
Deactivation
Coke
Bifunctional catalyst

a b s t r a c t
The deactivation causes have been studied for bifunctional catalysts used in the reforming of dimethyl
ether (DME). The kinetic runs have been carried out in a uidized bed reactor in the 275325 C range. The
bifunctional catalysts have been prepared using CuO-ZnO-Al2 O3 (of different formulations) as metallic
component, and HZSM-5 zeolites (of different acidity, moderated by desilication) as acid component. The
study has been carried out by jointly evaluating: (i) the evolution of reaction indices (conversion of DME
and methanol, and yields of H2 and hydrocarbon by-products) with time on stream, and; (ii) the proles
of temperature programmed oxidation for the coke deposited on the deactivated catalysts in order to
determine the content and location of the coke deposited; (iii) the physico-chemical properties of the
deactivated catalysts. The deactivation results for the catalysts used in the reaction have been compared
with those corresponding to the deactivation of the acid component in the step of DME hydrolysis and
the metallic component in the step of methanol reforming. It has been determined that coke deposition
on the metallic component is the main cause of the deactivation of bifunctional catalysts. This deposition
is enhanced by increasing temperature, although the incorporation of Al2 O3 in the formulation of the
metallic component in the catalyst attenuates the partial blockage of metallic sites by coke. Below 325 C,
there is no Cu sintering and its oxidation is not the cause of deactivation. Furthermore, the deposition of
coke on the acid component has a minor impact on deactivation.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Over the past decade, there has been increased interest in the
use of dimethyl ether (DME) as a fuel for H2 production in proton exchange membrane fuel cells (PEMFC), given that the steam
reforming of DME (SRD reaction) may be carried out at a relatively low temperature and has signicant advantages over the
use of methanol (MeOH), which are as follows: no toxicity, available logistics infrastructure (similar to LPG), higher H2 content
(13.0 wt% compared to 12.5 wt% of methanol), gas-like properties
and liquid storage density. Furthermore, the production of DME
is increasing through the progressive industrial implementation
of the single-step synthesis process (on a bifunctional catalyst),
whose thermodynamics is more favorable than that of methanol

synthesis [13]. Consequently, DME synthesis has better perspectives than methanol for co-feeding CO2 together with syngas [4].
Furthermore, the H2 /CO ratio required is lower, which is a positive
aspect for the viability of biomass gasication.
The SRD reaction does not occur on simply a metallic catalyst,
but requires a bifunctional catalyst prepared with two components,
one with acid sites (acid component) and the other one with metal
sites (metallic component). The reaction occurs in two steps in
series:
DME hydrolysis (on the acid sites):
(CH3 )2 O + H2 O 2CH3 OH
Methanol steam reforming (on the metal sites):
CH3 OH + H2 O 3H2 + CO2

Corresponding author. Tel.: +34 94 6015363; fax: +34 94 6013500.

E-mail address: javier.erena@ehu.es (J. Erena).


http://dx.doi.org/10.1016/j.apcata.2014.06.031
0926-860X/ 2014 Elsevier B.V. All rights reserved.

(1)

(2)

Thus, the presence of the metallic component in the catalyst shifts the thermodynamic equilibrium of DME hydrolysis,
and therefore gives rise to a positive effect on DME conversion.

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

Nomenclature
Cx Zy Az

CuO-ZnO-Al2 O3 metallic components prepared in


the laboratory with atomic ratios being x:y:z for
Cu:Zn:Al
Z(m)
HZSM-5 zeolite (SiO2 /Al2 O3 = 30) treated for
300 min with a m molar NaOH solution
Cc
coke content in the deactivated catalyst, %
average particle size of Cu, nm
d Cu
DME
dimethyl ether
dpore
average pore diameter,
Fi , Fi,0
molar ow rate of i component at the reactor outlet
and in the feed, respectively
Mcatalyst mass of catalyst (without coke), g
mass of CO2 , g
MCO2
MeOH methanol
PDME
DME partial pressure at the reactor inlet, bar
BET surface area, m2 /g
SBET
Scatalyst , SCu metal surface area, m2 /gcatalyst and m2 /gCu ,
respectively
steam reforming of DME
SRD
T
temperature, C
Vmeso , Vmicro mesopore and micropore volume, respectively,
cm3 /g
W
catalyst weight, g
XDME , XMeOH DME conversion and methanol effective conversion, respectively
molar fraction of hydrocarbons in the product
xHC
stream (without the inert He)
YH2
yield of hydrogen

Furthermore, the reverse water-gas shift reaction (r-WGS) generally takes place on the metallic component, especially at
temperatures above 300 C:
r-WGS reaction :

CO2 + H2 H2 O + CO

(3)

Methane (and to a lesser extent higher hydrocarbons) is also


generated via DME decomposition when high temperatures are
used [5], which is enhanced by the presence of strong acid sites
in the catalyst:
(CH3 )2 O CH4 + H2 + CO

(4)

Most of the studies dealing with DME steam reforming have


been carried out on catalysts containing a metallic component,
usually Cu-based oxides, mixed with an acid component, such as
-Al2 O3 [611], different zeolites [5,1219], and combined oxides
[2022]. Other metallic components have also been assayed, such
as Ga2 O3 and Ga2 O3 /Al2 O3 [23,24] and supported noble metals
[2527].
Zeolites have been proposed as an acid component in order
to promote the hydrolysis reaction at a lower temperature than
that required for -Al2 O3 . However, due to the presence of strong
acid sites, zeolites can also promote the reactions of hydrocarbon
and coke formation from DME and MeOH, which enhance catalyst
deactivation [5,15,18,28].
Consequently, suitable metallic and acid components are
required in the catalyst for high DME conversion, high H2 selectivity (avoiding the formation of CO, poison for the anode catalyst
in PEMFC, and CH4 ) and high stability, thereby operating for long
reaction periods without replacing the catalyst. Given the catalysts
kinetic performance is a consequence of the synergism between the
activities of the metallic and acid components, authors previous
studies paid especial attention to the attenuation of HZSM-5 zeolite
acidity [28], preparation and composition of the CuO-ZnO-Al2 O3

77

metallic component [29], as well as to the mass ratio between this


component prepared under the best conditions (Cu/Zn/Al atomic
ratio = 4.5:4.5:1.0) and the treated HZSM-5 zeolite, with the optimum zeolite/metallic component mass ratio being 1:1 [30].
Although catalyst stability is a key factor for process viability, it
has not been studied in depth in the literature. Therefore, this paper
focuses on the cause of deactivation and its relationship with catalyst properties and operating conditions. Based on the relevant
literature on the deactivation of bifunctional catalysts using CuOZnO-Al2 O3 (CZA) as the metallic component and HZSM-5 zeolites
(of different acidity) as the acid component, the possible causes of
the deactivation of these catalysts in the SRD reaction are as follows: (i) Cu sintering, above a threshold temperature [3133]; (ii)
coke deposition on the metal and/or acid active sites [12,14,19,21];
(iii) Cu oxidation, enhanced by the high steam concentration in the
reaction medium [20,33].
This paper addresses the cause of deactivation in the DME
reforming on bifunctional catalysts with CZA as metallic component and the HZSM-5 zeolite as acid component. Given its
signicance, a study has also been carried out of the effect the
main features of the catalysts components (composition of the
metallic component CZA and the acidity of the HZSM-5 zeolite)
as well as reaction temperature have on deactivation. Previous
papers [2830,34] reveal a signicant coke deposition, which has
been studied here by means of temperature programmed oxidation
(TPO), with the aim of determining the location of the coke and the
effect the composition of the metallic component and the acidity
of the zeolite have on coke deposition. This information on coke
deposition is used for explaining the results of catalyst deactivation and distinguishing the effect the coke deposited on each one
of the catalysts components has on the deactivation.

2. Experimental
2.1. Catalyst preparation and characterization
The metallic components of the catalysts, with different
Cu/Zn/Al atomic ratios, are prepared following a conventional
method based on coprecipitation [29,35]. Sodium carbonate
(Na2 CO3 10H2 O (Panreac, 99%)) is used for the precipitation of the
corresponding metallic nitrates (Cu(NO3 )2 3H2 O, Zn(NO3 )2 6H2 O
and Al(NO3 )3 9H2 O, (Panreac, 99%)), as it is the best agent for both
the coprecipitation of metallic components and the good control
of pH. The precipitation step is performed at 70 C with constant
pH (6.87.2), and it is followed by an ageing period of 1 h (under
the same conditions of pH and temperature). The resulting solid
is washed (as many times as necessary for completely removing
the alkaline cations) and subsequently dried in two steps (at room
temperature for 12 h and then at 110 C for another 12 h) and calcined (Thermicon P Heraeous, SA mufe) at 325 C for 3 h, following
a heating ramp of 5 C/min, in order to transform the metallic carbonates (precursors) into oxides. The metallic components have
been denoted as Cx Zy Az , with the subscripts x, y and z being the
atomic ratios corresponding to Cu/Zn/Al. The ratio values studied
are 1.0:1.0:0, 2.0:1.0:0 and 4.5:4.5:1.0. The addition of ZnO signicantly enhances Cu metal dispersion and avoids its sintering.
Furthermore, the addition of a small amount of Al2 O3 increases the
BET surface area and pore volume, thereby increasing the specic
metal surface area (Cu dispersion is enhanced) [29].
Three HZSM-5 zeolites have been used as acid component, with
two being prepared by treating a parent zeolite (SiO2 /Al2 O3 = 30,
supplied in ammonium form by Zeolyst International and denoted
as Z) with NaOH. The alkaline treatment of the HZSM-5 zeolite
has been carried out by immersion in a NaOH solution (0.2 or
0.4 M) at 80 C for 300 min, using a reux condenser to prevent

78

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

evaporation [28,36], followed by fast cooling and ion exchange


with an ammonium nitrate solution. The zeolite is subsequently
washed and dried in air for 24 h at room temperature and then at
110 C for another 24 h. The acid form is obtained after calcination
(Thermicon P Heraeous, SA mufe furnace) according to the following steps: ramp of 5 C min1 up to 400 C; 3 h at 400 C; ramp of
3.3 C min1 up to 450 C; 16 h at 450 C; ramp of 3.3 C min1 up
to 550 C; 3 h at 550 C and a cooling ramp of 4.4 C min1 to room
temperature. The acid components obtained by treating the zeolite with NaOH have been named Z(m), with m being the molar
concentration of NaOH used in the treatment. The treatment with
NaOH under moderate conditions causes HZSM-5 desilication, i.e.,
attenuation of the acid strength of the sites and mesopore formation (by opening micropores) [3638], which is an efcient way of
attenuating coke deactivation in the SRD reaction [28].
The bifunctional catalyst has been prepared by wet physical
mixing of metallic and acid component powders (previously calcined) in a mass ratio of 1:1, which is the optimum ratio for
maximizing DME conversion and H2 yield [30]. The resulting homogeneous mixture is dried at 110 C and then pressed, ground and
sieved to a particle size between 150 and 250 m.
The following properties have been analyzed for both the fresh
and deactivated catalysts: (i) reducibility, by means of temperature programmed reduction (TPR), carried out in a Micromeritics
AutoChem 2920; (ii) metal surface area and crystal size of Cu, by
N2 O chemisorption, in a Micromeritics AutoChem 2920 coupled
to a Balzers Instruments Omnistar mass spectrometer through a
thermostated line, for quantifying the N2 formed and the N2 O
not reacted with Cu according to the following stoichiometry:
N2 O + 2Cu Cu2 O + N2 ; (iii) BET surface area and porous structure,
by N2 adsorptiondesorption, in a Micromeritics ASAP 2010; (iv)
total acidity and acid strength distribution, by differential scanning
calorimetry of NH3 adsorption at 150 C carried out in a thermobalance (SDT 2960, TA Instruments) [39,40]. The total acidity
of the catalyst is the amount of base chemisorbed by mass unit,
whereas the acid strength distribution corresponds to the evolution with the mass of base chemisorbed of the heat released
by mass unit of chemisorbed base (determined by combining the
results of calorimetry and thermogravimetry for each incremental amount of adsorbed NH3 ). Accordingly, a decreasing trend in
the measurement means a selective adsorption, characteristic to
a heterogeneous acid strength distribution, i.e., the sites being
neutralized are from higher to lower acid strength. A horizontal
evolution corresponds to a uniform distribution, with sites having
the same acid strength [39,40]. Furthermore, it has been proven
that the acidity of the metallic components studied is insignicant, which evidences that the Al2 O3 contained does not have acid
properties.
The coke content deposited on the catalyst has been determined by temperature programmed oxidation (TPO) with air in
a thermobalance (TA Instruments SDT 2960) connected on-line to

a mass spectrometer (Balzers Instruments Thermostar) through a


thermostated line. The signals monitored in the spectrometer are
those corresponding to the combustion products (14, 18, 28 and 44
masses corresponding to N2 , H2 O, CO and CO2 , respectively), thus
avoiding combustion masking Cu oxidation in the thermobalance.
Coke combustion has proven to be complete (there is no signal for
mass 28 corresponding to CO), and the coke content in the deactivated catalysts has therefore been determined based on the catalyst
mass without coke (Mcatalyst ) and the CO2 formed (MCO2 , obtained
from the signal corresponding to CO2 ):

Cc (%) =

MCO2 12 gC /44 gCO2


Mcatalyst

100

(5)

Prior to coke combustion, the deactivated catalyst is subjected


to sweeping with He for 30 min in situ in the reactor itself at
the reaction temperature in order to desorb the reaction products and homogenize the coke [41]. The procedure based on
combustion in thermobalance has consisted in: (i) stabilizing the
sample for 30 min by passing an air stream at 75 C; (ii) heating the sample following a ramp of 5 C min1 up to 550 or
600 C, and keeping this temperature for 30 min for complete coke
combustion.

2.2. Reaction equipment and product analysis


The kinetic runs have been carried out in automated reaction
equipment (Microactivity Reference) provided with an isothermal
uidized-bed reactor with 22 mm of internal diameter connected
on-line to a Micro GC Agilent 3000 provided with four modules for the analysis of: (1) permanent gases (O2 , N2 , H2 , CO,
CH4 ); (2) oxygenates (MeOH, DME, CO2 ), light olens (C2 C3 )
and water; (3) C2 C6 hydrocarbons; (4) C6 C12 hydrocarbons and
oxygenate compounds. The hydrodynamic properties of the bed
have been improved by mixing the catalyst (particle size between
150 and 250 m) with inert alumina (particle size between 60
and 90 m) in a catalyst/inert ratio of 1:4. Data gathering and
processing are carried out using the software Soprane (Version
2.4.b).
Prior to the catalytic runs, the catalyst has been reduced in 10%
H2 in He at 300 C for 2 h with a total ow rate of 60 ml min1 .
The operating conditions are as follows: total pressure, 1.2 bar,
steam/DME/He molar ratio = 3:1:3.7 (or 4:1:0.55), space time up to
0.145 gcatalyst h/gDME , temperature in the 275325 C range. A definition has been given in Table 1 for the samples of deactivated
catalysts studied here, with the reaction conditions being also specied.

Table 1
Operating conditions in the runs corresponding to the catalysts used in the SRD reaction.
Sample

Catalyst

t, h

T, C

Steam/DME/He molar ratio

PDME , bar

W/FDME,0 , gcatalyst h/gDME

1
2
3
4
5*
6**
7
8
9

C4.5 Z4.5 A1 /Z(0.4)


C4.5 Z4.5 A1 /Z(0.4)
C4.5 Z4.5 A1 /Z
C4.5 Z4.5 A1 /Z(0.4)
C4.5 Z4.5 A1
Z(0.2)
C4.5 Z4.5 A1 /Z(0.2)
C1 Z1 A0 /Z(0.2)
C2 Z1 A0 /Z(0.2)

24
24
7
15
8
8
16
16
16

325
275
315
300
325
325
300
300
300

3:1:3.7
3:1:3.7
3:1:3.7
3:1:3.7
1.5:1:1a
3:1:3.7
4:1:0.55
4:1:0.55
4:1:0.55

0.155
0.155
0.155
0.155
0.343b
0.216
0.216
0.216
0.216

0.131
0.131
0.145
0.093
0.107c
0.149
0.145
0.145
0.145

*
**

Methanol steam reforming reaction: a = steam/MeOH/He molar ratio; b = PMeOH ; c = W/FMeOH,0


DME hydrolysis reaction.

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

2.3. Reaction indices

1.0

YH2 =

FDME,0 FDME
FDME,0
FH2

6 FDME,0

(6)

(7)

(8)

where FMeOH,0 is the methanol molar ow rate corresponding to


DME conversion, which is calculated as twice the number of DME
moles converted, according to the stoichiometry of DME hydrolysis
(Eq. (1)).

0.4

0.0

DME

MeOH

H2

Time on stream, h
1.0

b
0.8
(100) x Hc

FMeOH,0 FMeOH
FMeOH,0

0.6

0.2

where FDME,0 is the molar ow rate of DME at the reactor inlet;


FDME and FH2 are the DME and H2 molar ow rates, respectively,
at the reactor outlet, which are derived from the molar fractions
(calculated from chromatographic results) and the total molar ow
rate (determined by the atomic balances for H, C and O).
In order to quantify the activity of the metallic component in the
bifunctional catalyst, the methanol effective conversion has been
determined in the second step of the SRD process (i.e., methanol
steam reforming, Eq. (2)), XMeOH , as:
XMeOH =

0.8
X DME, X MeOH, YH2

In order to quantify the effect of deactivation, the reaction


indices, i.e., DME conversion (XDME ) and H2 yield (YH2 ), have been
calculated as follows:
XDME =

79

0.6
0.4
0.2

3. Results and discussion

0.0
3.1. Evolution of reaction indices and catalyst properties with
time on stream
3.1.1. Role of catalyst acidity in the deactivation
A previous paper [34] addresses the evolution of DME conversion, MeOH effective conversion and H2 yield with time on stream
for samples 1 and 2 in Table 1 (corresponding to the catalysts prepared using C4.5 Z4.5 A1 metallic component (Cu/Zn/Al = 4.5:4.5:1.0)
and the Z(0.4) zeolite (treated with 0.4 M NaOH for 300 min)),
for different temperatures and with a low value of space time
(0.131 gcatalyst h/gDME ), which has been chosen to clearly observe
the deactivation. The results evidence that temperature has a signicant effect on deactivation, and DME and MeOH conversions and
H2 yield decrease in a more pronounced way with time on stream as
temperature is increased, which is explained by the higher amount
of coke deposited.
A comparison of the aforementioned previous results [34]
(corresponding to the catalysts with the zeolite acid component subjected to alkaline treatment, Z(0.4)) with those (Fig. 1)
obtained using a catalyst with the same metallic component and
the parent zeolite Z (sample 3, in Table 1), shows that a higher
acidity and acid strength give rise to a faster decrease in DME
and methanol conversions with time on stream (Fig. 1a). Furthermore, it should be noted that hydrocarbons are formed as
by-products (Fig. 1b). This comparison of the results for the two
catalysts evidences the role of catalyst acidity in the hydrocarbon formation above 300 C, which has already been observed in
the literature [5,8,18,19,28]. Thus, hydrocarbon formation is signicant using the parent zeolite catalyst at 315 C, whereas it is
insignicant at 325 C with the desilicated zeolite based catalyst
[34].
The evolution of hydrocarbon molar fraction in the product
stream (without the inert He) with time on stream (Fig. 1b)
is explained by the hydrocarbon pool mechanism, which has
been established in the literature for the transformation of
methanol into hydrocarbons on different acid catalysts provided

Time on stream, h
Fig. 1. Evolution of DME conversion, MeOH effective conversion and H2 yield
(graph a) and molar fraction of hydrocarbons (graph b) with time on stream
for C4.5 Z4.5 A1 /Z catalyst in the SRD reaction (sample 3 dened in Table 1). Reaction conditions: 315 C; 1.2 bar; PDME , 0.155 bar; W/FDME,0 , 0.145 gcatalyst h/gDME ;
steam/DME/He molar ratio, 3:1:3.7.

with shape selectivity (SAPO-34 and HZSM-5 zeolite, amongst


others), with polymethylbenzenes being the intermediates for
olen formation (primary products) [4247]. The formation of
these intermediates requires an initiation period (1 h approximately in Fig. 1b, visualized when the scale is enlarged), with
hydrocarbons being formed from the end of this period and a
pseudo-steady state value being reached after 5 h, which for long
times is affected by the decrease in the catalysts capacity for
polymethylbenzene intermediate formation. Furthermore, hydrocarbon formation contributes to decreasing H2 yield with time on
stream (Fig. 1a).
A possible cause of catalyst deactivation is the deterioration of acidity by coke deposition. The fresh C4.5 Z4.5 A1 /Z(0.4)
catalyst has a total acidity of 0.36 mmolNH3 /gcatalyst , with the
main acid strength being around 110 kJ/molNH3 (Table 2). As
observed in Fig. 2, coke deactivation slightly decreases the
total acidity to 0.31 mmolNH3 /gcatalyst (sample 1) and the acid
strength is hardly affected. Furthermore, the fresh C4.5 Z4.5 A1 /Z
catalyst (prepared using the unmodied HZSM-5 zeolite) has a
higher total acidity (0.47 mmolNH3 /gcatalyst ), and a higher acid
strength (with sites mainly of around 125 kJ/molNH3 ). Its total acid
strength is only slightly affected by coke deactivation (decreases
to 0.39 mmolNH3 /gcatalyst , sample 3 in Fig. 2). Nevertheless, the
acid strength undergoes a signicant decrease, especially that
of the stronger acid sites, which evidences the role of the
very strong acid sites in coke deposition and their preferential
blockage.

80

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

Table 2
Effect of deactivation on the physical and acid properties of the catalysts (samples 13 dened in Table 1).
Catalyst

SBET , m2 /gcatalyst

Vmicropore , cm3 /gcatalyst

Vmesopore , cm3 /gcatalyst

dpore , A

Total acidity,
mmolNH3 /gcatalyst

Acid strength,
kJ/molNH3

C4.5 Z4.5 A1 /Z(0.4)


Fresh
Sample 1
Sample 2

207
193
198

0.041
0.031
0.033

0.330
0.320
0.311

82
86
88

0.36
0.31
0.32

110
107
108

C4.5 Z4.5 A1 /Z
Fresh
Sample 3

230
156

0.057
0.029

0.181
0.170

54
95

0.47
0.39

125
118

3.1.2. Deterioration of catalyst properties.


Table 2 sets out the physical properties (BET surface area, micropore and mesopore volume, and average pore size) and acidity
(total and average strength) for samples 13, corresponding to the
catalysts deactivated under the conditions in Table 1, together with
the values corresponding to the fresh catalysts. As observed, BET
surface area and micro and mesopore volume decrease (the latter
to a lesser extent) due to deactivation, whereas the average pore
size (determined by BJH method) increases. This means that micropores are partially blocked due to coke deposition, which is more
signicant for the parent HZSM-5 zeolite (sample 3), whose acidity
enhances coke formation, as has been well-reported for hydrocarbon transformation reactions [48]. Furthermore, both catalysts
undergo a decrease in total acidity and average acid strength due
to coke deposition.
3.1.3. Identication of the deactivation cause
The deterioration of catalyst acidity due to coke deposition
described in Section 3.1.1 may explain the decrease in DME conversion with time on stream (Fig. 1) because acidity is related to the
catalyst activity for DME hydrolysis (Eq. (1)). Nevertheless, it cannot explain the decrease in methanol conversion (also observed in
Fig. 1), which is related to the deterioration of the metallic component activity for methanol reforming (Eq. (2)). This deterioration of
the metallic component may be due to three possible causes affecting Cu sites, as are: (i) oxidation due to the oxidizing role of H2 O in
the reaction medium; (ii) sintering; (iii) blockage by coke deposition. In order to assess the contribution of each one of these three
causes to deactivation, runs have been carried out as described
below.
Firstly, in order to ascertain whether the cause of deactivation
is Cu oxidation, the catalyst has been subjected to a reduction

treatment for determining whether its metallic properties are


recovered. The catalyst used is sample 4 (dened in Table 1), which
has been subjected in situ to a reducing atmosphere (a stream with
10%, v/v H2 in He) at 300 C. Fig. 3 shows that this treatment does not
restore catalyst activity, given that DME and MeOH conversions at
the beginning of the second cycle are almost the same as those corresponding to the end of the rst reaction cycle. This result means
that the partial oxidation of Cu throughout the reaction is not the
cause of deactivation, which is consistent with the results by Liu
et al. for Cu/CeO [20], and by Faungnawakij et al. for Cu spinel [8].
Furthermore, it has been proven that this reduction treatment does
not contribute to decreasing the coke content in the deactivated
catalyst.
Furthermore, the analyses by TPR (Fig. 4) show that the metallic components active sites have a slightly lower reducibility due
to deactivation. These analyses have been carried out on the fresh
and deactivated catalysts once they have been oxidized under an
air stream. A comparison of the TPR proles in Fig. 4 for the fresh
and deactivated catalysts (samples 13 in Table 1) shows that all
the samples record a characteristic peak (around 190 C) corresponding to Cu2+ reduction, whose position and amplitude depend
on the metal oxidationreduction state, metalsupport interaction
and extent of site dispersion [49]. There are no signicant differences between the proles for the fresh and deactivated catalysts,
although the curves for the deactivated ones are slightly shifted
towards higher temperatures. As will be shown below, the cause is
not sintering, but the partial blockage of the metallic sites by coke,
thus hindering H2 access and Cu2+ reduction.
Table 3 shows the results of N2 O chemisorption for the fresh and
deactivated catalysts (samples 13 dened in Table 1) and for sample 1 once it has been regenerated by coke combustion with diluted
air at 300 C until the complete removal of the coke deposited on

250

200

0.8
Sample 3
C4.5Z4.5A1/Z

150

XDME, XMeOH

Acid strength, kJ (molNH3)

-1

100
Sample 1
C4.5Z4.5A1/Z(0.4)

50

0.1

0.2

st

nd

0.6

Reaction

XDME
XMeOH

0.4
0.2

0.3

0.4

0.5

mmolNH3 (gcatalyst)-1
Fig. 2. Distribution of the acid strength for deactivated catalysts (samples 1 and
3 dened in Table 1). Reaction conditions: 1.2 bar; PDME , 0.155 bar; W/FDME,0 ,
0.131 gcatalyst h/gDME (sample 1), 0.145 gcatalyst h/gDME (sample 3); steam/DME/He
molar ratio, 3:1:3.7.

12

15

Time on stream, h
Fig. 3. Effect of catalyst reduction with H2 between the reaction cycles on the evolution of DME and MeOH conversions with time on stream for C4.5 Z4.5 A1 /Z(0.4)
catalyst (sample 4 dened in Table 1). Reaction conditions: 300 C; 1.2 bar; W/FDME,0 ,
0.093 gcatalyst h/gDME ; PDME , 0.155 bar; steam/DME/He molar ratio, 3:1:3.7.

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

-1

sample 1
sample 2

100

150

200

250

0.4

1.2

0.3

0.8

0.2

0.4

0.1

100

200

300

400

500

600

0
700

Temperature, C
Fig. 5. Comparison of the TPO proles for Z(0.2) acid component used in DME
hydrolysis (sample 6), C4.5 Z4.5 A1 metallic component used in the SRMeOH reaction
(sample 5), and for the bifunctional catalyst deactivated in the SRD reaction (sample
3 dened in Table 1).

TCD signal, a.u.

0.5

1.6

300

Temperature, C

C4.5Z4.5A1/Z

-1

-1

CO2, mols (gcatalyst)

TCD signal, a.u.

fresh

0.6
Z(0.2)
C4.5Z4.5A1
Sample 3

-1

2.4

CO2, mols (gcatalyst)

C4.5Z4.5A1/Z(0.4)

81

established as the catalyst calcination temperature for avoiding sintering. Based on the results mentioned above, deactivation is not
caused by Cu oxidation and/or sintering, and only coke deposition
is responsible for the decrease in metal surface area with time on
stream.

fresh
sample 3

3.2. Coke deposition analysis by TPO

100

150

200

250

300

Temperature, C
Fig. 4. Effect of deactivation on TPR proles for C4.5 Z4.5 A1 /Z(0.4) catalyst (graph
a) and C4.5 Z4.5 A1 /Z catalyst (graph b) (samples 1-3 dened in Table 1). Reaction
conditions: 1.2 bar; PDME , 0.155 bar; W/FDME,0 , 0.131 gcatalyst h/gDME (samples 1 and
2), 0.145 gcatalyst h/gDME (sample 3); steam/DME/He molar ratio, 3:1:3.7.

the metallic sites. As mentioned above, coke is not removed in a


H2 /He stream. Prior to N2 O chemisorption, the samples are subjected to in situ reduction in a stream of H2 /Ar (10% H2 ) at 260 C
for 2 h.
A comparison of the metallic properties of the fresh and deactivated catalysts (samples 13) in Table 3 shows a signicant
decrease (by almost half) in the metal surface area (both specic
area, SCu (by mass unit of Cu in the catalyst) and total area, Scatalyst
(by mass unit of the bifunctional catalyst)) and an increase in the
metal particle size due to deactivation. Nevertheless, once it has
been regenerated (by removing the coke deposited on the metallic
component), the value of the metal surface area is similar to that of
the fresh catalyst, which means that Cu sintering in the reaction is
not the cause of deactivation under the conditions studied (reforming temperature of 325 C or lower). Consequently, 325 C has been
Table 3
Effect of catalyst deactivation and regeneration by coke combustion on the properties of the catalysts metallic component (samples 13 dened in Table 1).
Catalyst

SCu , m2 /gCu

Scatalyst , m2 /gcat

d Cu , nm

C4.5 Z4.5 A1 /Z
Fresh
Sample 3

56
40

10
7

12
16

C4.5 Z4.5 A1 /Z(0.4)


Fresh
Sample 1
Sample 2
Sample 1 (regenerated)

56
30
36
56

10
5
6
10

12
22
18
12

Given the signicance coke deposition has on deactivation, it has


been studied in detail by means of TPO analysis in order to determine coke content and location, and ascertain the coke deposited
on the metallic and acid components in the catalysts. This analysis
is interesting for obtaining information on coke structure (heterogeneity, condensation and H/C ratio) and its location in the
catalysts porous structure [5052].
3.2.1. Identication of the coke in the catalyst components
In order to determine the cokes location in the catalyst for the
SRD reaction and the role each one of the catalyst components plays
in coke formation, TPO proles have been studied for the following samples: (i) the catalyst used in the SRD reaction (sample 3
in Table 1); (ii) the metallic component used in the reforming of
methanol (sample 5); and (iii) the acid component used in DME
hydrolysis (sample 6). Fig. 5 shows the TPO proles for sample 3,
for the acid component (Z(0.2) treated HZSM-5 zeolite) used in DME
hydrolysis at 325 C (in order to obtain a signicant coke deposition), and for the C4.5 Z4.5 A1 metallic component used in the steam
reforming of methanol at 325 C. The TPO proles for samples 1
and 2, corresponding to the catalysts deactivated in SRD reaction
under different conditions [34], are shown in the supplementary
information.
Firstly, signicant differences are observed in the results in Fig. 5
corresponding to coke content (area under the curve) for different
catalysts, reactions and operating conditions. Secondly, a major difference is found between the proles corresponding to the metallic
(C4.5 Z4.5 A1 ) and acid (Z(0.2)) components used in the reactions
of methanol reforming and DME hydrolysis, respectively. Furthermore, the proles for the catalysts used in the SRD reaction are a
combination of those corresponding to the individual reaction steps
and depend on reaction conditions and catalyst properties.
The TPO prole in Fig. 5 for the C4.5 Z4.5 A1 catalyst (sample 5,
metallic component used as catalyst in the reforming of methanol,
whose coke content is 3.6 wt%) shows a prevailing combustion
peak at around 220 C corresponding to a uniform and amorphous
coke [8], which is deposited on Cu metallic sites [12,20]. The low

82

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

Table 4
Effect of Al2 O3 in the catalysts metallic component on the decrease in DME and MeOH conversions and H2 yield subsequent to 16 h time on stream in the SRD reaction
(samples 79 dened in Table 1) [29].

16 h

0.632
0.566
0.361

0.596
0.460
0.278

5.6
18.7
23.0

combustion temperature is explained by the combustion of the


coke deposited on the Cu-ZnO metallic phase being activated by the
oxidizing capacity of Cu being as Cu2+ , which is attained when an O2
stream is passed through the catalytic bed. This peak is observed in
the combustion of the coke deposited on this type of metallic component used in the DME synthesis [51,52]. A shoulder at a slightly
higher temperature (250 C) is attributed here to the combustion
of a coke fraction deposited on the Al2 O3 supporting the metallic
component.
The TPO prole for Z(0.2) catalyst (sample 6, acid component
used as catalyst in DME hydrolysis, whose total coke content is
4.3 wt%) shows that coke starts to burn above 250 C, and two
characteristic peaks appear in the combustion: (i) one at around
410 C, which corresponds to a coke that is easily burnt (slightly
condensed) and O2 is easily accessed (presumably deposited on
the mesopores outside the microporous zeolite crystals), and; (ii)
another one at above 500 C, corresponding to a more condensed
coke (with a lower H/C ratio) and deposited presumably on the
microporous zeolite crystals. Shimoda et al. have obtained similar
TPO proles in the combustion of different zeolites used in DME
hydrolysis [19].
The TPO proles for samples 13 (corresponding to the
bifunctional catalysts used in the SRD reaction) are consistent with
the results in the literature for the bifunctional catalysts for reforming [8,12,21], i.e., two main coke types are usually identied: (i)
the peak at a low temperature (210250 C), corresponding to
the coke deposited on the metallic component, and (ii) the peak
at an intermediate temperature (350450 C), deposited on the
acid component. A third coke type is also observed under severe
deactivation conditions, which is presumably highly condensed
(graphitic nature) and burns above 500 C. This coke is presumably deposited on the acid component and its combustion is not
directly catalyzed by the metallic sites [53].
The TPO proles for the catalysts deactivated in the SRD reaction (samples 13) also record these two main peaks, although their
features depend on the properties of the acid component. As mentioned when explaining the results in Fig. 1, the acid strength of
the HZSM-5 zeolite used as acid component in the catalyst significantly affects catalyst deactivation, which is caused by the higher
coke deposition. Thus, for sample 3 (prepared using the parent zeolite), the peak at higher temperature is much more pronounced
than for the samples 1 and 2 (catalyst containing desilicated zeolite)
(TPO proles in the supplementary information). Consequently, the
coke contents in samples 3 and 1 are 1.2 wt% and 0.5 wt%, respectively. Furthermore, the third peak mentioned above (540 C) is
also observed for sample 3, which corresponds to the combustion
of a condensed coke fraction deposited at the mouth of the zeolite micropores and whose development is activated by Brnsted
sites of high acid strength [48]. The signicant content of coke on
the metallic component in sample 3 explains the faster decrease in
methanol conversion with time on stream (Fig. 1a).
Based on these results (TPO proles in Fig. 5 and the evolution of reaction indices with time on stream in Fig. 1 and in
a previous paper [34]), the main cause of catalyst deactivation
in the SRD reaction is the deposition of coke on the metallic
sites, which is higher as reaction temperature is raised. The coke

XMeOH

XMeOH (%)

0h

16 h

0.960
0.922
0.786

0.940
0.873
0.679

YH2

2.1
5.3
13.6

YH2 (%)

0h

16 h

0.624
0.538
0.293

0.554
0.410
0.172

11.2
23.8
41.3

is presumably formed by the degradation of methoxy ion intermediates derived from the oxygenates in the reaction medium
[34,52].
Furthermore, although the deactivation of the acid component
has a smaller impact on the SRD reaction, as reported in the
literature using different catalysts [12,14,21], it should be considered and avoided by moderating catalyst acidity by treating the
HZSM-5 zeolite in order to minimize very strong acid sites, which
are those favoring coke formation. Therefore, although the main
cause of deactivation is coke deposition on the metallic component, the aforementioned values of high coke deposition on the
acid component in sample 3 suggest that also this coke may contribute to decreasing the reaction indices with time on stream
(Fig. 1).
3.2.2. Role of the catalysts metallic component composition in
coke deposition
Given the signicance of the metallic component in the deactivation in the SRD reaction [29,30], the effect the composition of
this component has on coke deactivation has been studied. Table 4
shows the values at zero time on stream and after 16 h time on
stream of DME and MeOH conversions and H2 yield (together with
the change in the percentages of these reaction indices in 16 h)
for three catalysts. These results have been obtained in a previous
study [29] in which the good behavior of the metallic component
used in this paper was proven. The catalysts have been prepared
with the same acid component (Z(0.2) zeolite) and C4.5 Z4.5 A1 ,
C1 Z1 A0 and C2 Z1 A0 metallic components. Fig. 6 shows the TPO analysis of the coke deposited on samples 79, corresponding to these
catalysts once they have been used in the steam reforming of DME
at 300 C (Table 1).
Table 4 shows that the catalysts without Al2 O3 in the metallic
component (samples 8 and 9) deactivate slightly faster than the
catalyst with Al2 O3 in their metallic component (sample 7), which
has also been observed by Kawabata et al. [14]. The rate of decrease
0.1

-1

XDME (%)

0h

Cc, wt%
0.07
0.08 0.09
0.1

sample 7
sample 8
sample 9

0.06

-1

C4.5 Z4.5 A1 /Z(0.2)(Sample 7)


C1 Z1 A0 /Z(0.2) (Sample 8)
C2 Z1 A0 /Z(0.2) (Sample 9)

XDME

CO2, mols (gcatalyst)

Catalyst

0.04
0.02
0
100

200

300

400

500

600

Temperature, C
Fig. 6. Effect of Al2 O3 in the catalysts metallic component on the TPO proles for
the bifunctional catalysts used in the SRD reaction (samples 79 dened in Table 1).
Reaction conditions: 300 C; 1.2 bar; PDME , 0.216 bar; W/FDME,0 , 0.145 gcatalyst h/gDME ;
steam/DME/He molar ratio, 4:1:0.55.

A.G. Gayubo et al. / Applied Catalysis A: General 483 (2014) 7684

in the conversions with time on stream for the different catalysts


is related to coke deposition on the metallic component (peak at
200250 C in the TPO proles in Fig. 6). This peak is smaller for
the catalyst with Al2 O3 in the metallic component (sample 7) and
shifts towards lower combustion temperatures than those for the
peaks corresponding to the catalysts with the metallic components
without Al2 O3 (samples 8 and 9). This difference is attributed to
the attenuation of coke formation on the metallic sites due to both
the presence of Al2 O3 (dispersion of metallic crystallites) and the
location of the growing coke on the Al2 O3 mesopores, which also
attenuates the blockage of CuO-ZnO metallic sites.
These results have been complemented with those for N2 O
chemisorption, which evidence that the decrease in the metal surface area is more pronounced for the deactivated catalysts without
Al2 O3 in the metallic component (39 and 42% for samples 8 and
9, respectively) than for the catalysts with Al2 O3 in their metallic
component (28% for sample 7).
4. Conclusions
The overall interpretation of the experimental results of deactivation for CuO-ZnO-Al2 O3 /HZSM-5 bifunctional catalysts in the
reforming of DME and of the TPO proles for the coke deposited on
the catalysts is that the main cause of deactivation is coke deposition on the metallic component.
Coke deposition leads to a deterioration in the properties of the
porous structure, i.e., the BET surface area and micro- and mesopore
volume decrease, and the average pore diameter increases (blockage of part of the micropores). There is also a slight decrease in the
total acidity of the catalyst, and when the HZSM-5 zeolite used has a
high acid strength there is a slight decrease in this strength. Nevertheless, deactivation is related mainly to the decrease in the metal
surface area due to the partial blockage of CuO-ZnO metallic sites
by coke, and this deactivation is faster as temperature is raised in
the 275325 C range due to the enhancement of coke formation.
It has been proven that Cu does not undergo sintering below
325 C (there is no reduction in the metallic surface area once coke
has been removed by combustion with air at 300 C), and neither
does the possible oxidation of Cu throughout the reaction contribute to catalyst deactivation (a reduction treatment does not
restore catalyst activity).
It should be noted the TPO proles reveal the existence of two
coke fractions deposited on the metallic sites and on the HZSM-5
zeolite micropores, with acidity moderation being a key factor for
attenuating coke deposition. The desilication by alkaline treatment
is suitable for this purpose, i.e., coke deposition on the acid component has a secondary impact on catalyst deactivation. Furthermore,
the addition of Al2 O3 in the formulation of the metallic component
helps to attenuate the deposition of coke on this component and is
efcient for attenuating the partial blockage of the metallic sites by
coke.
Acknowledgements
This work has been carried out with nancial support from the
Basque Government (Project IT748-13), the Ministry of Science and
Technology of the Spanish Government (Projects CTQ2009-13428
and CTQ2012-35263), and the University of the Basque Country
(UFI 11/39).
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.apcata.
2014.06.031.

83

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