Monitoring Ni0 and Coke evolution during the Deactivation of a Ni/La2O3-αAl2O3

Catalyst in Ethanol Steam Reforming in a fluidized bed

Carolina Montero*, Aitor Ochoa, Pedro Castaño, Javier Bilbao, Ana G. Gayubo

Supplementary Information

Calculation of diffusion limitations by applying the Weisz-Pratter and Mears

Weisz-Prater Criterion for Internal Diffusion [48]

 r ' A( obs)  c R 2
If CW P   1 , then internal mass transfer effects can be neglected.
De C As

-r’A(obs) = observed reaction rate, kmol/kg-cat·s= 6.4x10-5 (TOS=0h)-2.54x10-5(TOS=20h)

R = catalyst particle radius, m=7.5x10-5-1.25x10-4 (average=1x10-4)

ρc = solid catalyst density, kg/m3 = 2476.4 (determined by mercury porosimetry)

De = effective gas-phase diffusivity, m2/s =7.73x10-6

D AB p c
= where


DAB = gas-phase diffusivity m2/s=8.07 x10-5 (calculated by Chapman-Enksog kinetic teory)

 p = pellet porosity= 0.48 (determined by mercury porosimetry)

 c =constriction factor = 0.8 (Fogler)

 =tortuosity= 4.5± 0.5 (Castro and Becerra, 1998)

CAs = gas concentration of A at the catalyst surface, kmol-A/m3=3.92 x10-3

 r ' A( obs)  c R 2
CW P  = 5.24 x 10-2 (TOS=0h) – 2.08 x 10-2 (TOS=20h) < 1
De C As
Mears Criterion for External Diffusion [48]

 rA '  b Rn
If  0.15 , then external mass transfer effects can be neglected.
k c C Ab

n = reaction order =4

ρb = bulk density of catalyst bed, kg/m3=1291

kc = mass transfer coefficient, m/s =2.04 ( calculated based in Sherwood, Reynolds and
Schmit adimensional correlations)

 rA '  b Rn
= 7.66x10-4(TOS=0h) - 3.03x10-4 (TOS=20h) < 0.15
k c C Ab

Ni0 Ni 0
Ni+2 Ni +2
Ni+2
Intensity, u.a

Ni0 Ni+2

Ni0

890 880 870 860 850 840

Binding Energy, eV

Figure S1. High resolution XPS spectra of Ni2p for the reduced fresh catalyst.
 150
time , h
0
120 4
8
20
Vads,cm3g-1

90

60

30

0
0 0.2 0.4 0.6 0.8 1

P/P0

Figure S2. N2 adsorption-desorption isotherms for the fresh catalyst (0 h) and for the catalyst
deactivated for different time on stream values
Figure S3. FTIR spectra of the fresh and spent catalyst after 20 h on stream.