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Page 1: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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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: [email protected]; 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

Page 2: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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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

Page 3: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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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

Page 4: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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Figure S2.

10 m

A1 A2

B1 B2

C1 C2

D1 D2

Page 5: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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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

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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

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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

Page 8: regeneration cyclic operation for catalyst life extension ... · the optimized reaction/regeneration cyclic procedure employing 10 vol.% of O2 in the regeneration step and re-carburating

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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