Deactivation of catalyst

during steam reforming of

Model Bio-Oil
Presented by:
Hemlata Malav
Priyanka Gupta
Sanjana Mandrai
Shubam Gupta
Vinita Kumari

Steam reforming over various

catalyst

Rioche C., Kulkarni S., Meunier F. C., Breen J. P., Burch R. ,Steam reforming of model
compounds and fast pyrolysis bio-oil on supported noble metal catalysts, Applied
Catalysis B: Environmental 61 (2005) 130139

 In absence of catalyst the major products were CO2

and CH4 with only minor fractions of CO and H2. The
extent of the reaction increased with temperature and
at 7540 C, almost 76% of the acetic acid was
converted, with a 37% CO2 yield and 31% CH4 yield.
In the presence of the noble metal catalysts, the main
changes being the lowering of the selectivity to CH4
and a large increase in the proportion of CO and H2.
The ceriazirconia supported catalysts almost
completely suppressed the conversion to CH4 (yield <
1%), while a significant concentration of CH4 was
observed over the Al2O3-supported samples.
The 1% Pt-CeZrO2, 1% Rh-CeZrO2 and 1% Rh-Al2O3
catalysts were the most active and selective for H2
and COx formation, with (CO + CO2) yields up to 89%.
These samples had comparable hydrogen yield, i.e. up
to ca. 66%
The Pd-catalysts performed poorly in terms of COx and

3.5
3
2.5
molar flow rate(kmol/s)
2
methane output

1.5

CO_output
CO2
Hydrogen output

H2O_output

0.5
0

713 793 873 953 1033

673 753 833 913 993 1073
temperature(k)

100
90
80
70
60
Yield,selectivity
50

H2 selectivity
H2 yield

40
30
20
10
0
600

700

800

900

temp(in kelvin)

1000

1100

70
60
50

CO
selectivity

40

CO2
selectivity

selectivity
30

CH4
selectivity

20
10
0
600

700

800
900
temp(in kelvin)

1000

1100

Possible reactions
CH3COOH+2 H2O CO2+4H2 (131.4
kj/mol)
2CH3COOHCH3COCH3+CO2+H2O
(-165.1kj/mol)
CO+H2O CO2 + H2 (-41KJ/mol)
CO+3H2 CH4 + CO2 (-206.1KJ/mol)
CO2 + 4H2 CH4 +2H2O (-165.1KJ/mol)
CH3COOH2CO+2H2 (213.4KJ/mol)
CH4 + H2O CO+3H2 (206 KJ/mol)

50
45
40
35
30
yield,selectivity 25

H2 yield
H2 selctivity

20
15
10
5
0
1

s/c ratio

Catalyst Deactivation
Catalyst deactivation during steam
reforming of
acetic acid over Pt/ZrO2
2CH3COOHCH3COCH3+CO2+H2O
2CH3COCH3(CH3)2C(OH)CH2COCH3
(diacetone
alcohol)(CH3)2CCHCOCH3(mesityl
oxide)+H2O
(CH3)2CCHCOCH3

 (CH3)2CCHCOCH3
(CH3)C=CH2(isobutene)
C2=,C3=(oligomers)
CH3COOHCH2CO+H2O(ketene
formation)
2CH2CO C2H4 + 2CO
2CH2CO C3H4 + CO2

Kazuhiro Takanabe, Ken-ichi Aika, K. Seshan, Leon Lefferts, Catalyst deactivation during
steam reforming of acetic acid over Pt/ZrO2, Chemical Engineering Journal, Volume 120,
Issues 12, 1 July 2006, Pages 133-137, ISSN 1385-8947

Deactivation model
The kinetics of both the main reaction and
the coking reactions are intimately
connected
The monolayermultilayer coke growth
model is used to describe the coke
formation kinetics
Coke content in the catalyst is described
by taking into account a simultaneous
formation of coke over the surface of the
catalyst and a multilayer coke deposition

Total coke formation

Monolayer

Multilayer

CT is the total coke concentration at any time

Cm coke concentration in monolayer
CM , multi-layer
Cmax maximum coke concentration in monolayer
k1 and k2 are rate constants given by Arrhenius
expression
h, n, m are constant

The equations were solved for different

combinations of {h,n,m}.
The final values obtained from best fit were
h=1, n= 1 and m= 0.
For these values of h, n and m, the above set
of equations were simplified into following
equations after integration

V. Agarwal, Sanjay Patel, K.K. Pant, H2 production by steam reforming of methanol over
Cu/ZnO/Al2O3 catalysts: transient deactivation kinetics modeling, Applied Catalysis A:
General, Volume 279, Issues 12, 28 January 2005, Pages 155-164, ISSN 0926-860X