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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
(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.
Nomenclature
Cx Zy Az
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)
(4)
77
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
Cc (%) =
100
(5)
Table 1
Operating conditions in the runs corresponding to the catalysts used in the SRD reaction.
Sample
Catalyst
t, h
T, C
PDME , bar
1
2
3
4
5*
6**
7
8
9
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
*
**
1.0
YH2 =
FDME,0 FDME
FDME,0
FH2
6 FDME,0
(6)
(7)
(8)
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
0.8
X DME, X MeOH, YH2
79
0.6
0.4
0.2
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.
80
Table 2
Effect of deactivation on the physical and acid properties of the catalysts (samples 13 dened in Table 1).
Catalyst
SBET , m2 /gcatalyst
dpore , A
Total acidity,
mmolNH3 /gcatalyst
Acid strength,
kJ/molNH3
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
250
200
0.8
Sample 3
C4.5Z4.5A1/Z
150
XDME, XMeOH
-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.
-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).
0.5
1.6
300
Temperature, C
C4.5Z4.5A1/Z
-1
-1
fresh
0.6
Z(0.2)
C4.5Z4.5A1
Sample 3
-1
2.4
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
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.
SCu , m2 /gCu
Scatalyst , m2 /gcat
d Cu , nm
C4.5 Z4.5 A1 /Z
Fresh
Sample 3
56
40
10
7
12
16
56
30
36
56
10
5
6
10
12
22
18
12
82
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
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
XDME
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.
83
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