Post on 24-Aug-2020
1
Non-oxidative dehydroaromatization of methane: an effective reaction-
regeneration cyclic operation for catalyst life extension
M. Teresa Portilla1, Francisco J. Llopis2, Cristina Martínez1*
1Instituto de Tecnología Química (UPV-CSIC), Universidad Politécnica de Valencia-Consejo Superior
de Investigaciones Científicas, Av. de los Naranjos s/n, 46022 Valencia, Spain.2Departamento de Ingeniería Química, Universitat de Valencia, 46100 Burjassot, Spain
* Corresponding author: cmsanche@itq.upv.es; Tel.: (34) 963877811, FAX: (34) 963879444
Figure S1. X-Ray diffraction (XRD) patterns of (A) ZSM-5, (B) IM-5, (C) TNU-9 and (D) MCM-22 before
and after the molybdenum loading
Figure S2. SEM pictures of Mo/ZSM-5 (A1, A2), Mo/IM-5 (B1, B2), Mo/TNU-9 (C1, C2) and
Mo/MCM-22 (D1, D2), employing a secondary electron (SE) detector (figures on the left), and a
backscatter electron (BSE) detector (figures on the right). Si and Al are showed in gray scale while
Mo particles correspond to white dots.
Figure S3. Methane conversion (A), summatory of yield to HC products (B), selectivity to aliphatics
(C), to aromatics (D), to benzene (E) and to naphthalene (F) versus time-on-stream over Mo/ZSM-5
when the carburation step (previous to the reaction) is started at room temperature ( ) or at 723K
( )
Figure S4. Methane conversion (A), total yield to HC products (B) and selectivity to benzene (C) for
the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration
step and re-carburating the catalyst after the calcination ( ) in comparison with 18h TOS MDA
reaction ( ) over Mo/IM-5
Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2015
2
Figure S5. Methane conversion (A), total yield to HC products (B) and selectivity to benzene (C) for
the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration
step and re-carburating the catalyst after the calcination ( ) in comparison with 18h TOS MDA
reaction ( ) over Mo/TNU-9
Figure S6. Methane conversion (A), total yield to HC products (B) and selectivity to benzene (C) for
the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration
step and re-carburating the catalyst after the calcination ( ) in comparison with 18h TOS MDA
reaction ( ) over Mo/MCM-22
3
Figure S1.
0 5 10 15 20 25 30 35 40
2 (degree)
MCM-22
Mo/MCM-22
5 10 15 20 25 30 35 40
2 (degree)
TNU-9
Mo/TNU-9
0 5 10 15 20 25 30 35 40
2 (degree)
IM-5
Mo/IM-5
(C) (D)
(A) (B)
0 5 10 15 20 25 30 35 40
2 (degree)
ZSM-5
Mo/ZSM-5
4
Figure S2.
10 m
A1 A2
B1 B2
C1 C2
D1 D2
5
Figure S3.
0
4
8
12
16
20
0 2 4 6
CH4
Conv
ersi
on (%
)
TOS (h)
A
0
2
4
6
8
10
0 2 4 6
S Yi
eld
to H
C pr
oduc
ts (C
wt.%
)
TOS (h)
B
0
5
10
15
20
25
0 2 4 6
Sele
ctiv
ity to
Alip
hatic
s (C
wt.%
)
TOS (h)
C
75
80
85
90
95
100
0 2 4 6
Sele
ctiv
ity to
Aro
mat
ics (
C w
t.%)
TOS (h)
D
50
60
70
80
90
100
0 2 4 6
Sele
ctiv
ity to
Ben
zene
(C w
t.%)
TOS (h)
E
0
10
20
30
40
50
0 2 4 6
Sele
ctiv
ity to
Nap
htha
lene
(C w
t.%)
TOS (h)
F
6
Figure S4.
0
4
8
12
16
20
0 5 10 15 20
CH4
Conv
ersi
on (%
)
TOS (h)
A
0
2
4
6
8
10
0 5 10 15 20To
talY
ield
to H
C (C
wt.%
)TOS (h)
B
50
60
70
80
90
100
0 5 10 15 20
Sele
ctiv
ity to
Ben
zene
(C w
t.%)
TOS (h)
C
7
Figure S5.
0
4
8
12
16
20
0 5 10 15 20
CH4
Conv
ersi
on (%
)
TOS (h)
A
0
2
4
6
8
10
0 5 10 15 20To
tal Y
ield
to H
C (C
wt.%
)TOS (h)
B
50
60
70
80
90
100
0 5 10 15 20
Sele
ctiv
ity to
Ben
zene
(C w
t.%)
TOS (h)
C
8
Figure S6.
0
4
8
12
16
20
0 5 10 15 20
CH4
Conv
ersi
on (%
)
TOS (h)
A
0
2
4
6
8
10
0 5 10 15 20To
talY
ield
to H
C (C
wt.%
)TOS (h)
B
50
60
70
80
90
100
0 5 10 15 20
Sele
ctiv
ity to
Ben
zene
(C w
t%)
TOS (h)
C