mesoporous ni-ceo2-zro2-sio2 composite catalyst …hai.org.in/pdf/conference_ppts/day3/1_sunil...
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Mesoporous Ni-CeO2-ZrO2-SiO2 composite catalyst for
steam reforming of n-butanol
Associate Professor, Department of Chemical Engineering, Indian Institute of Technology
Hyderabad, Kandi, Sangareddy-502285, Telangana, India.
Email: [email protected]
By
Dr. Sunil K. Maity
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Background of the work Experimental
Results and discussion
Conclusions
Motivation and overview
Experimental set up, catalyst preparation & characterization, and definition of variables
Catalyst characterizationSteam reforming of n-butanol
Summary of the work
Outline
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Global Energy Scenario
• 80% of energy comes from fossil
fuel
• 90% of organic chemicals are
derived from petroleum
Oil32.8%
Coal27.2%
Natuaral gas20.9%
Nuclear 5.8%
Hydro2.3%
Biofuels and waste10.2%
Others*0.8%
Renewable recourses
• Biomass
Background of the work
3
Key world energy statistics. International Energy Agency, 2011
Synthesis gas (CO+H2)
• Ammonia and fertilizers
• Fischer-Tropsch synthesis of methanol & dimethyl ether
• Fuel cell
• Source: Naphtha and natural gas
Bio-butanol
• Compatible with gasoline engines
Production of syngas from bio-butanol
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Catalyst carrier: Ceria
• Oxygen storage/release property
• Low surface area
• Thermally unstable
• Prone to sintering at high temperature
Catalyst carrier: CeO2-ZrO2 mixed oxide
• Improved thermal stability
• Enhances oxygen storage capacity due to the formation of lattice defects
• Thermally unstable at high calcination temperature
• Low surface area
Background of the work
4
Steam reforming over Ni-CeO2-ZrO2-SiO2
composite catalyst
Catalyst carrier: Zirconia
• High hardness
• Good mechanical resistance
• High thermal stability
Catalyst carrier: CeO2-ZrO2-SiO2 mixed oxide
• High surface area
• Thermally stable Low surface area
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Experimental Catalyst Preparation:
Evaporation-induced self-assembly method
• Silica was 70 wt%
• Abbreviation: xNiCaZbS where a and b are the mole ratio of CeO2
and ZrO2 and x represents wt% of nickel in the catalyst.
Catalyst characterization:
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ExperimentalFixed-Bed Reactor Catalysis Science and Technology Lab.
Gas products
• H2, N2, CO, CO2, CH4
• CH4, ethane, ethylene, propane,
propylene, butanes, and butylenes
Liquid products
• Propanal, butanal
rateof moleof water fedS/C moleratio=
7 rateof moleof n-butanolfed
Steam reforming reaction
C4H10O +7H2O 4CO2 +12H2
2 4
Carbon conversion to synthesis gas (CCSG),%
rate of mole of CO+CO +CH formed100
rate of mole of carbon fed
Hydrogen yield, %
rate of mole of hydrogen formed100
12 (rate of mole of n-butanol fed) (fractional conversion of n-butanol)
Definition of variables
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Catalysts SA PV dp20NiC0Z3S 263 0.21 3.2620NiC1Z2S 237 0.22 3.63
20NiC1.5Z1.5S 210 0.18 3.3920NiC2Z1S 192 0.18 3.60
SA = specific surface area, m2/g; PV = pore volume, cm3/g; dp =pore size, nm
Catalyst characterization
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Qu
an
tity
ad
so
rbe
d (
cm
3/g
ST
P),
a.u
.
Relative pressure, P/Po
20NiC0Z
3S
20NiC1Z
2S
20NiC1.5
Z1.5
S
20NiC2Z
1S
2 3 4 5 6 7 8 9 10
dV
/dlo
g(D
) p
ore
vo
lum
e (
cm
3/g
A0),
a.u
.
Pore diameter, nm
B1
20NiC0Z
3S
20NiC1Z
2S
20NiC1.5
Z1.5
S
20NiC2Z
1S
Nitrogen adsorption-desorption
isotherm
Pore size distribution
BET surface area (Calcined catalyst)
TEM image
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Catalyst characterization Powdered XRD pattern (Calcined catalyst)
Chemisorption and Ni crystallite size
and
Reduced catalyst
10 20 30 40 50 60 70 80
# ZrO2
###
#
CeZrO2
©
©©©
©
NiO€
€€€€€
2, deg
Inte
nsi
ty, a
.u.
20NiC2Z
1S
20NiC1.5
Z1.5
S
20NiC1Z
2S
20NiC0Z
3S
10 20 30 40 50 60 70 80
©©©
ZrO2
#
### #
CeZrO2
©
©
Ni*
***
Inte
nsi
ty, a
.u.
20NiC2Z
1S
20NiC1.5
Z1.5
S
20NiC1Z
2S
20NiC0Z
3S
2, deg
CATALYSTS MD SM dc, nm (Ni)20NiC0Z3S 0.09 0.62 33.120NiC1Z2S 0.88 5.86 21.6
20NiC1.5Z1.5S 0.72 4.82 23.120NiC2Z1S 0.74 4.91 23.7
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Catalyst characterization Temperature programmed reduction
400 500 600 700 800 900 1000 1100
CeO2
ZrO2
Temperature, K
951K
20NiC2Z
1S
20NiC1.5
Z1.5
S
20NiC1Z
2S
20NiC0Z
3S
NiO
TC
D s
ign
al, a
.u.
815K860K597K
635K
705K
698K
686K
670K
773K
Bulk NiO
Surface ceria
Bulk ceria
Dispersed NiO
Dispersed NiO (inside mesopores)
Reduction of Ce4+ to Ce3+
NiO incorporated in the structure
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Steam reforming of n-butanol Role of CeO2/ZrO2 mole ratio on the catalytic performance
0
20
40
60
80
100
Selectivity
to BUY, %
Conversion of n-butanol, %CCSG, %
Selectivity to CO2, %
Selectivity
to CH4, %
Selectivity
to CO, %
A 20NiC0Z
3S 20NiC
1Z
2S
20NiC1.5
Z1.5
S 20NiC2Z
1S
H2 yield, %
0.0
0.2
0.4
0.6
0.8
1.0
1.8
2.0
2.2
Ethane, % Propane, %
Propylene, %
Butanes, %
Propanal, %
Butanal, %
Sele
cti
vit
y t
o h
yd
rocarb
on
s, %
B 20NiC0Z
3S 20NiC
1Z
2S
20NiC1.5
Z1.5
S 20NiC2Z
1S
Reaction conditions: 873K, 8.79h-1 WHSV, and 2.5 S/C mole ratio.
CATALYSTS MD SM dc, nm (Ni)20NiC0Z3S 0.09 0.62 33.120NiC1Z2S 0.88 5.86 21.6
20NiC1.5Z1.5S 0.72 4.82 23.120NiC2Z1S 0.74 4.91 23.7
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Steam reforming of n-butanol Effect of nickel loading on the catalytic performance
Reaction conditions: 873K, 8.79h-1 WHSV, and 2.5 S/C mole ratio.
0
5
10
15
20
60
80
100 25NiC
1Z
2S 30NiC
1Z
2S
Conversion of n-butanol, %CCSG, %
10NiC1Z
2S 15NiC
1Z
2S 20NiC
1Z
1S
Selectivity
to BUY, %
Selectivity
to CO2, %
Selectivity
to CH4, %
Selectivity
to CO, %
A
H2 yield, %
0.0
0.1
0.2
0.3
0.4
1
2
3
4
5
25NiC1Z
2S 30NiC
1Z
2S
10NiC1Z
2S 15NiC
1Z
2S 20NiC
1Z
2S
Sel
ecti
vit
y t
o h
yd
rocarb
on
s, %
Ethane, % Propane, % Propylene, % Butanes, %
B
CatalystsChemisorption
dc, nmRed
MD SM Ni10NiC1Z2S 0.95 6.34 17.315NiC1Z2S 0.85 5.70 18.520NiC1Z2S 0.88 5.86 21.625NiC1Z2S 0.23 1.56 41.430NiC1Z2S 0.21 1.42 44.3
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Steam reforming of n-butanol Time-on-stream behavior of 20NiC1Z2S
Reaction conditions: 873K, 8.79h-1 WHSV, and 2.5 S/C mole ratio.
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
0
5
10
15
20
25
70
80
90
100
Time-on-stream, h
Selectivity to CO, %
Selectivity to CH4, %
Hydrogen yield, %
Selectivity to CO2, %
CCSG, %
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Conclusions
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THANK YOU