The solid with 15% of Ni and 0,5% of Ru (S_0,5Ru) showed the best catalytic behaviour in all the studied compositions and also the lowest amount of carbon ...
Ru – Ni CATALYSTS FOR CO2 CONVERSION USING METHANE REFORMING REACTIONS
Andrea Álvarez, Miguel Ángel Centeno, José Antonio Odriozola Instituto de Ciencia de Materiales de Sevilla, Centro Mixto Universidad de Sevilla - CSIC. Avenida Americo Vespucio 49, 41092, Sevilla, Spain
A
% 1 1
!
' '
!"#$$%&'$
H2/CO=1 HOW TO PRODUCE SYNGAS WITH A H2/CO 2 ?
H2O ADDITION !!
Catalysts design
Catalyst Characterization
Calcined samples
THE PROGRAMMING ! -Al2O3
Formation of MgAl2O4 spinel:
Ruº
NiMAlu 2%Ru/MgAl2O4
[101] [111]
[200]
Niº MgAl2O4
Niº
[400]
S_2Ru
#"N No evidence of Ru as (RuO2) or (Ruº)) in the sample S_0,5Ru. !
S_0,5Ru NiMAlu 2%Ru/MgAl2O4
Suggests highly disperses Ru!
0,5%Ru/MgAl2O4
!" Increases H2O and CO2 adsorption. !" Increases basicity. !" Increases Ni dispersion.
[002]
XRD
S_0,5Ru
Intensity (a.u)
-Al2O3
Reduced samples
Ruº
S_2Ru
MgAl2O4
Syntheti ze activ e and stabl e Ni base d catalysts for severa l C O2 c o nversio n reactions
SYNGAS
Among the many human activities that produce green house gases (GHG) the use of energy represents by far the largest source of emissions. Within the energy sector, CO2 resulting from the oxidation of carbon in fuels during combustion, correspond to the 90% of produced GHG.
!"#$%&'&% ()*%
!
CH4 + CO2 ! 2 CO + 2 H2
'
69%
PURPOSE
$
%'
Energy
14%
0,5%Ru/MgAl2O4 MgAl2O4
MgAl2O4 20
25
30
35
40
45
50
55
º2!
60
65
70
75
40
42
44
46
48
º2!
50
52
54
LO TO
RAMAN STUDY
S_0,5Ru
S_2Ru S_0,5Ru NiMAlu 2%Ru/MgAl2O4
#" Suggests higher Ru-Ni interaction
S_2Ru
200
300
THERMODYNAMIC ANALYSIS
2,0
80
Thermodynamic Eq.
S_0,5Ru
70
S_2Ru
60
NiMAlu
50 40 30
POST-REACTION ANALYSIS
1,8
900 800 700
80
0,3
H2O CO2/CH4 : 0,6
0
10
20
30
Time (h)
40
80
60
70
50 40 30
50
NiMAlu
0
Thermodynamic Eq.
S_2Ru
70
S_2Ru
S_0,5Ru
S_0,5Ru
NiMAlu
50 40 30 20 10
20
30
40
50
10
15
20
Time (h)
50
50 S_2Ru
30
S_0,5Ru
30
10
30
Time (h)
500 NiMAlu
S_0,5Ru
40
50
400
60
70
300
80
Time (min)
0
20
+
40
60
80
900
9% H 2O
13% H 2O
800
20% H 2O
28% H2O
70
700 600
S_0,5Ru
500
S_2Ru
NiMAlu
400
S_0,5Ru
56
60
63 Time (min)
300 77
70
900
50
800
40
S_2Ru
30
10
20
S_2Ru
50
NiMAlu
20
NiMAlu
0
600
S_2Ru
40
90
60
800 700
Time (h)
70
10
S_0,5Ru
80
40
28% H 2O
60
10
25
80
20 0
5
20% H2O
662ºC
569ºC
20
Thermodynamic Eq.
90
60
10
70
13% H2O
9% H 2O
595ºC
NiMAlu
0
20
40 Time (h)
60
80
S_0,5Ru
700 600
NiMAlu
500 S_2Ru
400
50
60
70
Time (min)
Conclusions "" The solid with 15% of Ni and 0,5% of Ru (S_0,5Ru) showed the best catalytic behaviour in all the studied compositions and also the lowest amount of carbon deposits after 100h of reaction. "" Water addition to the reaction not only helped the carbon gasification, and therefore the activity, but also was very useful to modulate the final H2/CO ratio obtained. "" An optimum molar ratio of 1-0,56-0,4 of CH4-H2O-CO2 was found to achieve the production of syngas with H2/CO ratio of 2, a feedstock very useful in Fisher-Tropsch reaction for the manufacture of synthetic fuels.
80
300
Temperature (ºC)
CO2 conversion (%)
1,4
90
90
900
Temperature (ºC)
CO2/CH4 : 0,4
Molar Ratio CO2/CH4: 0,4 +
10
CO2 conversion (%)
10
0,5
Temperature (ºC)
900
Thermodynamic Eq.
20
20
0,6
800
Molar Ratio CO2/CH4: 0,4
90
CH4 conversion (%)
CH4 conversion (%)
80
2,2
0,7
400 500 600 700 -1 Raman Shift (cm )
100 200 300 400 500 600 700 800 900
Temperature (ºC)
H2/CO
Molar Ratio CO2/CH4: 1
90
2,4
0,8
2%Ru/MgAl2O4
CATALYTIC RESULTS
CO2/CH4: 0,2
0,4
NiMAlu
0,5%Ru/MgAl2O4
MgAl2O4
1,6
S_0,5Ru
0,5%Ru/MgAl2O4
Calcined at 500ºC for 3h!
2,50 2,35 2,20 2,05 1,90 1,75 1,60 1,45 1,30
S_2Ru
CO2 --> m/z=44 signal (a.u)
NiMAlu
#
#"R Ru O 2 l a t t i c e seems to b e a ff e c t e d b y NiO presence.!
#"T The presence of Ru increases the reducibility of Ni and decreases the temp erature of reduction.!
O2 --> m/z=32 signal (a.u)
!"
!" #
TP R – H 2
CO --> m/z=28 signal (a.u)
!"#$%&%$
A1g B2g
CH4 conversion (%)
!" #
'("$)*+$,#$%&%$
Eg
CO2 conversion (%)
!"#$%&%$
T (ºC)
Others
COULD WE USE CO2 AS A FEEDSTOCK ?
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6%
Intensity (a.u)
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