Steam Reforming of Ethane and
Ethanol over Rh/Alumina:
a comparative study.
Muhammad Bilal1, Claire Gillan1, Sam French2,
Martin Fowles2 and S David Jackson1
1Centre
for Catalysis Research, WestCHEM, University of Glasgow, Glasgow G12 8QQ, Scotland, UK
Matthey plc, Belasis Ave, Billingham TS23 1LB UK
2Johnson
Steam Reforming
O2/N2
Naphtha
Steam Reforming
Hydrogen
Ammonia
Steam Reforming
O2/N2
Naphtha
Steam Reforming
Hydrogen
Ammonia
Syngas
Methanol
Steam Reforming
Natural
gas
O2/N2
Steam Reforming
Hydrogen
Ammonia
Syngas
Methanol
Steam Reforming
Natural
gas
O2/N2
Steam Reforming
Hydrogen
Ammonia
Syngas
Methanol
Fischer
Tropsch
Steam Reforming
Natural
gas
O2/N2
Biomass
Steam Reforming
Hydrogen
Ammonia
Syngas
Methanol
Fischer
Tropsch
Ethane Steam Reforming
Steam Reforming
CnH2n+2 + nH2O
nCO + (2n+1)H2
Water Gas Shift
CO + H2O
CO2 + H2
Hydrogenolysis
C2H6 + H2
2CH4
Methanation
CO + 3H2
CH4 + H2O
Ethanol Steam Reforming
Ethanol decomposition
C2H5OH
CO + CH4 + H2
Ethanol steam reforming
C2H5OH + H2O
2CO + 4H2
Ethanol dehydration
C2H5OH
C2H4 + H2O
Ethanol dehydrogenation
C2H5OH
CH3CHO + H2
Experimental
Catalyst: 0.2 % Rh/Al2O3
Temp: 873 K
GHSV: 49,000
H2O:C2H6 /C2H5OH 5:1
Pressure: 20 barg
100
Ethanol steam
reforming over
alumina support
Conversion (%)
80
60
40
20
0
2
7.5
27.5
31.5
55.5
74.5
Time on stream (h)
79.5
100
Alumina selectivity
45
% Yield
36
27
18
9
0
23.5
47.5
71.5
Time on stream (hrs)
CH4
H2
CO2
CO
C2H6
C2H4
100
Ethanol Steam Reforming
Ethanol decomposition
C2H5OH
CO + CH4 + H2
Ethanol steam reforming
C2H5OH + H2O
2CO + 4H2
Ethanol dehydration
C2H5OH
C2H4 + H2O
Ethanol dehydrogenation
C2H5OH
CH3CHO + H2
Ethanol Steam Reforming, alumina
Ethanol decomposition
C2H5OH
CO + CH4 + H2
Water Gas Shift
CO + H2O
CO2 + H2
Alumina selectivity
45
% Yield
36
27
18
9
0
23.5
47.5
71.5
Time on stream (hrs)
CH4
H2
CO2
CO
C2H6
C2H4
100
0.25
-0.003
0.2
-0.0035
0.15
-0.004
0.1
-0.0045
0.05
-0.005
0
0
100
200
300
400
500
600
700
Temperature (C)
Derivative weight
44
800
900
-0.0055
1000
Ion current (m/e 44)
Derivative weight
Alumina
Rh/alumina, 873 K
100
Conversion (%)
80
60
40
20
0
0.0
5.0
10.0
15.0
Time on stream (h)
Ethane
Ethanol
20.0
25.0
Ethane, Rh/alumina
Molar dry gas
selectivity
32.8%
37.9%
14.5%
H2
14.9%
CO
CO 2
CH4
Ethanol, Rh/alumina
Molar dry gas
selectivity
7%
4%
15%
51%
15%
8%
H2
CO
CH4
CO2
C2H4
C2H6
Ethanol, 873 K
12
Yield (%)
10
8
6
4
2
0
24
48
72
100
Time on stream (h)
Ac e ta ldehyde
DE E
Acetone
1,1-DiethoxyE
2C2H5OH + H2O  CH3COCH3 + CO2 + 4H2
2CH3CHO  CH3CH(OH)CH2CHO
CH3CH(OH)CH2CHO + O(s) 
CH3CH(OH)CH2COO(s) + H(s)
CH3CH(OH)CH2COO(s) + H(s)  CH3COCH3
+ CO2 + H2
Molar Selectivity (%)
60
50
40
30
20
10
0
H2
CO
CH4
Ethanol
CO2
Ethane
C2H4
C2H6
15
CO + CH4 + H2
CO2 +
H2
15
+H2O
+H2O
C2H5OH
4
CO + H2
11
C2H6
4
+H2
C2H4 +
H2O
CO + H2
14
1
CH4 + H2O
+2H2
+H2O
+2H2O
CO2 +
H2
15
C2H6
16
+H2
CH4
‐3.00E‐03
‐0.0318
‐0.032
‐3.50E‐03
‐0.0322
‐4.00E‐03
‐0.0326
‐0.0328
‐4.50E‐03
‐0.033
‐0.0332
‐5.00E‐03
‐0.0334
‐0.0336
‐5.50E‐03
‐0.0338
0
100
200
300
400
500
600
Temperature (C)
Rh/alumina
Alumina
700
800
900
1000
ion current, m/e 44
ion current. m/e 44
‐0.0324
8000
1594
1344
Intensity (a.u.)
6600
5200
3800
2400
1000
100
600
1100
1600
2100
Raman shift (cm-1)
600C
2600
3100
3600
4100
CONCLUSIONS
Ethane:
 No significant catalyst deactivation at 873 K
 No evidence for filaments
 High methane selectivity
 O:C ratio in products, ~4:6
Ethanol:
 No significant deactivation at 873 K
 Filament formation
 High hydrogen selectivity
 O:C ratio in products, ~5:6
CONCLUSIONS
Ethane:
 Simpler reaction sequence
 No evidence for synthesis
Ethanol:
 Complex reaction sequence
 Synthesis as well as deconstruction
CONCLUSIONS
Ethane:
 primary reactions, steam reforming & hydrogenolysis
 secondary reactions, WGS & methanation
Ethanol:
 primary reactions, ethanol dehydration, ethanol
decomposition, steam reforming, ethanol
dehydrogenation, acid catalysis
 secondary reactions, WGS & ethene hydrogenation,
synthesis reactions
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