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Thermodynamic Analyses of Adsorption-Enhanced Steam Reforming of Glycerol For Hydrogen Production
Thermodynamic Analyses of Adsorption-Enhanced Steam Reforming of Glycerol For Hydrogen Production
Thermodynamic Analyses of Adsorption-Enhanced Steam Reforming of Glycerol For Hydrogen Production
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abstract
Article history:
steam reforming of glycerol for hydrogen production based on the principle of minimising
the Gibbs free energy. The effects of temperature (6001000 K), pressure (14 bar), water to
25 June 2009
glycerol feed ratio (3:112:1), percentage of CO2 adsorption (099%) and molar ratio of
carrier gas to feed reactants (1:15:1) on the reforming reactions and carbon formation are
examined. The results show that the use of a CO2 adsorbent enhances glycerol conversion
to hydrogen and the maximum number of moles of hydrogen produced per mole of glyc-
Keywords:
erol can be increased from 6 to 7 due to the CO2 adsorption. The analyses suggest that the
Hydrogen production
most favourable temperature for steamglycerol reforming is between 800 and 850 K in the
presence of a CO2 adsorbent, which is about 100 K lower than that for reforming without
Adsorption-enhanced
CO2 adsorption. Although high pressures are favourable for CO2 adsorption, a lower
reaction process
operating pressure gives a higher overall hydrogen conversion. The most favourable water
Thermodynamic analyses
to glycerol feed ratio is found to be w9.0 above which the benefit becomes marginal.
Carbon formation
Carbon formation could occur at low water to glycerol feed ratios, and the use of a CO2
adsorbent can suppress the formation reaction and substantially reduce the lower limit of
the water to glycerol feed ratio for carbon formation.
2009 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights
reserved.
1.
Introduction
7209
(1)
If the reaction is equilibrium-limited, the glycerol conversion and the rate of the forward reaction can be enhanced by
removing CO2 as soon as it is formed from the reaction zone.
Sorption enhanced reaction processes have been the subject
of numerous investigations since the 1980s [7]. Among the
published work, the sorption enhanced steam reforming of
methane is of particular relevance to the current work, which
has been demonstrated both theoretically and experimentally
[810]. It was found in these studies that the operating
temperature can be reduced substantially from around 1000 K
to about 700 K by using an adsorbent. One of the objectives of
this work is, therefore, to find out the level of temperature
reduction for steamglycerol reforming if a CO2 adsorbent is
used. From an economic point of view, the use of a 9:1 water to
glycerol feed ratio (S/C 3:1) is high. It is also known that
reduction in the ratio can lead to the formation of carbon. As
a consequence, another important objective of the current
work is to find out if the use of a sorption enhanced reaction
process can alleviate such a problem. A combination of stoichiometric and non-stoichiometric thermodynamic analyses
will be used to achieve the above objectives, which are based
on the minimisation of Gibbs free energy for chemical reactions. Such analyses will also provide information for optimal
operating conditions to guide further experimental work.
This paper is structured in the following manner. Section 2
gives the details of the fundamentals associated with the
analyses. The results are then discussed in Section 3 and
finally conclusions are summarised in Section 4.
2.
Theoretical considerations
2.1.
Non-stoichiometric approach
(2)
N
X
mi dni
N
X
mi dni
(4)
i1
N
X
mi n i
(5)
i1
aji ni bj ;
j 1; .; M
(6)
i1
N
X
i1
mi ni
M
X
j1
lj
N
X
!
(7)
aji ni bj
i1
dG
(3)
0
M
X
vG
mi
lj aji 0;
vni T;P;nj si
j1
i 1; .; N
M
X
lj aji 0;
i 1; .; N
(9)
(10)
j1
or
i1
(8)
bi
DGi =RT lnni =nT ln P ln f
M
X
j1
7210
nT
N
X
ni ;
i 1; .; N
(11)
i1
2.2.
Molar fraction
1.2 108
1.3 109
1.5 109
1.0 1011
2.0 1011
2.0 1013
9.4 1013
2.0 1013
1.5 1015
6.7 1015
Methanal (CH2O)
Methanol (CH3OH)
Ethylene (C2H4)
Ethane (C2H6)
Ethanal (CH3COH)
Ethanol (C2H5OH)
Propane (C3H8)
Propene (C3H6)
Propanal (CH3CH2CHO)
Propanone (CH3COCH3)
nC DGC 0
(12)
GCf is
the Gibbs
where nC is the number of moles of carbon, and
free energy of carbon formation, which is zero. However, the use
of Equation (12) can lead to numerical instabilities due to
a difference in the numbers of unknowns and equations [12,19].
To avoid this numerical issue, carbon formation is investigated
by using a combined method of non-stoichiometric and stoichiometric thermodynamic analyses. Calculations are first
conducted using the non-stoichiometric methodology with
a high water to glycerol feed ratio with which the carbon
formation is unlikely to occur. The resulting species mole fractions are then used to investigate stoichiometrically the
7
6
Molar Number
5
4
3
2
1
0
600
700
800
900
1000
Temperature (K)
Fig. 1 Equilibrium compositions: comparison between
this work and Ref [6] for T [ 6001000 K, P [ 1 bar and
WGFR [ 9:1.
7211
8
H2
H2
6
CH4
CO2
Molar Number
Molar Number
CH4
CO
CO
4
3
2
4
3
2
0
1
0
0.0
0.2
0.4
0.6
0.8
1.0
Pressure (bar)
Fig. 2 Equilibrium compositions: effect of pressure for
T [ 800 K, P [ 14 bar, and WGFR [ 9:1.
(13)
CH4 2H2 C
(14)
CO H2 H2 O C
(15)
(16)
(17)
(18)
(19)
(20)
7
H2
6
CH4
CO
Molar Number
CO2
4
3
2
1
0
12
7212
1.8
1.5
f=0.0
f=0.0
1.5
f=0.2
f=0.2
1.2
f=0.4
f=0.6
1.2
Molar Number
Molar Number
f=0.4
f=0.8
f=0.99
0.9
f=1.0
0.6
f=0.6
f=0.8
0.9
f=0.99
f=1.0
0.6
0.3
0.3
0.0
0.0
600
700
800
900
600
1000
700
1.0
f=0.2
900
1000
f=0.6
f=0.8
0.6
900
1000
1.0
0.8
f=0.4
Decrement
Decrement
0.8
f=0.99
f=1.0
0.4
0.6
0.4
0.2
0.2
0.0
600
700
800
900
1000
0.0
600
700
where Ki (i 1316) are the equilibrium constants for Reactions (13)(16) respectively and yi is the mole fraction of
component i (i CO, CO2, CH4, H2O). For steamglycerol
reforming, carbon formation is possible when the maximum
of the four activities, AC, is greater than unity:
AC maxA13 ; A14 ; A15 ; A16 > 1
(21)
CO2 adsorption
800
Temperature (K)
Temperature (K)
2.3.
800
Temperature (K)
Temperature (K)
(22)
f=0.2
f=0.6
f=0.99
f=0.4
f=0.8
f=1.0
f
b i lC 2lO =RT0
DGCO2 =RTln nCO2 $1f =nT lnPln f
(23)
N
X
ni nCO2 $f ;
i 1; .; N
(24)
i1
2.4.
7213
3.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
1.0
2.5
0.8
2.0
Increment
Molar Number
1.2
f=0.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
1.5
1.0
0.5
0.0
600
700
800
900
0.6
0.4
0.2
0.0
1000
600
700
Temperature (K)
800
900
1000
900
1000
Temperature (K)
3.0
1.0
2.5
Decrement
Molar Number
0.8
2.0
1.5
1.0
0.5
0.6
0.4
0.2
0.0
600
700
800
900
1000
0.0
600
700
Temperature (K)
f=0.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
800
Temperature (K)
f=1.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
Fig. 8 Carbon dioxide production and remaining CO2: effect of temperature for P [ 1 bar and WGFR [ 9:1, (a) Number of
moles of CO2 production, (b) Relative increment in CO2 production, (c) Number of moles of remaining CO2, (d) Relative
decrement in the remaining CO2.
(25)
f
b i 2lN =RT 0
DGN2 =RT ln nN2 =nT ln P ln f
(26)
2.5.
Numerical calculations
7214
1.5
f=0.4
f=0.6
f=0.0
f=0.2
f=1.0
f=0.8
f=0.99
1.2
Molar Number
Molar Number
6
5
4
3
2
0.6
0.3
1
0
0.9
f=0.0
f=0.4
f=0.8
f=0.2
f=0.6
f=0.99
f=1.0
0.0
4
Pressure (bar)
Pressure (bar)
2.0
f=0.2
1.0
f=0.4
f=0.6
1.5
0.8
f=0.99
Decrement
Increment
f=0.8
f=1.0
1.0
0.6
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
0.4
0.2
0.5
0.0
0.0
Pressure (bar)
Pressure (bar)
3.
3.1.
Steamglycerol reforming in the absence of
adsorption
Calculations were first conducted on the steam reforming of
glycerol without adsorption for which thermodynamic data are
available for comparison [6,16]. Fig. 1 compares the calculated
Molar Number
3.2.
Steamglycerol reforming with CO2 adsorption for
typical sets of conditions
0.5
f=0.4
f=0.6
f=0.0
f=0.2
0.4
f=1.0
f=0.8
f=0.99
0.3
0.2
0.1
0.0
1
Pressure (bar)
1.0
f=0.2
f=0.4
Decrement
0.8
f=0.6
f=0.8
7215
f=0.99
f=1.0
0.6
0.4
0.2
0.0
3.3.
Effect of temperature on adsorption-enhanced
hydrogen production
1
Pressure (bar)
Fig. 11 Carbon monoxide production: effect of pressure
for T [ 800 K and WGFR [ 9:1, (a) Number of moles, (b)
Relative decrement.
7216
3.0
1.0
f=0.2
f=0.4
f=0.99
f=1.0
f=0.6
f=0.8
0.8
Increment
Molar Number
2.7
2.4
2.1
0.4
0.2
1.8
f=0.4
f=0.6
f=0.0
f=0.2
1.5
0.6
f=0.8
f=0.99
f=1.0
0.0
Pressure (bar)
3.0
f=0.4
f=0.6
f=0.0
f=0.2
2.5
f=0.8
f=0.99
f=1.0
1.0
f=0.2
f=0.4
0.8
f=0.99
f=1.0
f=0.6
f=0.8
2.0
Decrement
Molar Number
Pressure (bar)
1.5
1.0
0.5
0.6
0.4
0.2
0.0
0.0
1
Pressure (bar)
Pressure (bar)
Fig. 12 Carbon dioxide production: effect of pressure for T [ 800 K and WGFR [ 9:1, (a) Number of moles, (b) Increment, (c)
Number of moles of remaining CO2, (d) remaining CO2 decrement.
7217
1.2
f=0.0
f=0.2
f=0.8
f=0.99
f=1.0
0.9
Molar Number
Molar Number
f=0.4
f=0.6
5
4
3
0.6
0.3
f=0.4
f=0.6
f=0.0
f=0.2
f=0.8
f=0.99
f=1.0
0.0
12
2.0
b
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
1.5
12
1.0
0.8
Decrement
Increment
1.0
0.6
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
f=1.0
0.4
0.5
0.2
0.0
0.0
3
12
12
3.4.
Effect of pressure on adsorption-enhanced hydrogen
production
The effect of pressure on hydrogen production is illustrated in
Fig. 9(a) and 9(b) for T 800 K and WGFR 9:1 (S/C 3:1). For
a given pressure, both the number of moles of hydrogen at
equilibrium and relative change (increment) in the amount of
hydrogen production increase with increasing fractional CO2
removal (Fig. 9(a)). For a given fractional CO2 removal, the
amount of hydrogen produced decreases with increasing
pressure, whereas the relative change (increment) in the
amount of hydrogen production due to CO2 adsorption (RCH2 )
shows an opposite trend (Fig. 9(b)). A comparison of the results
7218
f=0.4
f=0.6
f=0.0
f=0.2
0.4
Molar Number
0.5
f=1.0
f=0.8
f=0.99
0.3
0.2
0.1
3.5.
Effect of water to glycerol feed ratio (WGFR) on
adsorption-enhanced hydrogen production
0.0
3
12
b
1.0
f=0.2
f=0.4
Decrement
0.8
f=0.6
f=0.8
f=0.99
f=1.0
0.6
0.4
0.2
0.0
12
shown in Fig. 9(a) and 9(b) suggests that low pressure operations are favourable for hydrogen production, in agreement
with the results in the absence of CO2 adsorbent.
Fig. 10 shows the effect of pressure on methane production
for T 800 K, and WGFR 9:1 (S/C 3:1). For a given operating
pressure, the equilibrium amount of methane decreases with
increasing fractional CO2 adsorption (Fig. 10(a)), whereas the
relative change (decrement) in the equilibrium amount shows
an opposite trend (Fig. 10(b)). With increasing pressure, the
equilibrium amount increases (Fig. 10(a)) but the relative
change (decrement) in the equilibrium amount decreases
(Fig. 10(b)), if the fractional CO2 removal is fixed. These results
suggest that low pressures are more favourable for hydrogen
production through steamglycerol reforming; this is in
agreement with the results shown in Fig. 9.
The effect of pressure on carbon monoxide production is
illustrated in Fig. 11 for T 800 K and WGFR 9:1 (S/C 3:1).
The number of moles of carbon monoxide is seen to decrease
with increasing fraction of CO2 adsorption for a given operating pressure, and decrease with increasing pressure if the
fraction of CO2 adsorption is fixed. However, the relative
change (decrement) in CO production (RCCO) is almost
7219
3.0
1.0
f=0.2
f=0.4
f=0.99
f=1.0
f=0.6
f=0.8
0.8
Increment
Molar Number
2.7
2.4
2.1
1.8
1.5
f=0.0
f=0.2
f=0.4
3
f=0.6
f=0.8
f=0.99
0.4
0.2
f=1.0
0.6
0.0
12
3.0
f=0.4
f=0.6
f=0.0
f=0.2
2.5
f=0.8
f=0.99
12
f=1.0
1.0
f=0.2
f=0.4
0.8
f=0.99
f=1.0
f=0.6
f=0.8
2.0
Decrement
Molar Number
1.5
1.0
0.5
0.6
0.4
0.2
0.0
3
12
0.0
12
Fig. 16 Carbon dioxide production: effect of water to glycerol feed ratio for T [ 800 K and P [ 1 bar, (a) Number of moles, (b)
Increment, (c) Number of moles of remaining CO2, (d) Decrement in the remaining CO2.
3.6.
Carbon formation
The results for carbon formation are shown in Fig. 17(a) and
17(b) for various fractions of CO2 removal through adsorption
at two pressures of 1 bar and 4 bar, respectively. The figures
give the zero carbon formation curves, which correspond to
AC being equal to unity. The region on the left side of the zero
carbon curves is where carbon formation may occur and that
on the right side is the carbon-free region.
Consider first Fig. 17(a) for 1-bar operation, where the
results can be split into three groups according to the fractional CO2 removal ( f ):
Group I ( f w0.4) - For this group, the minimum water to
glycerol feed ratio (above which no carbon in theory would
form) decreases with increasing temperature given a CO2
removal fraction. For example, the minimum water to
7220
a 1000
Carbon Region
P=4bar, f=0.0
Molar Number
Temperature (K)
900
6
No Carbon Region
800
f=0.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
700
600
H2
CO
CO2
3
2
1
0
CH4
800
f=0.0
f=0.2
f=0.4
f=0.6
f=0.8
f=0.99
700
0.8
1.0
5
4
3
2
1
0
0.0
0.2
carbon curves for 1 bar are included in Fig. 17(b) and those
for 4 bar are also given in Fig. 17(a). One can see that the
difference between the zero carbon curves at the two
pressures is small, indicating a weak pressure effect on
carbon formation. The results shown in Fig. 17(a) and 17(b)
clearly demonstrate that the use of CO2 adsorption
suppresses carbon formation at temperatures below about
900 K.
3.7.
P=1bar, f=0.0
600
No Carbon Region
Molar Number
900
Temperature (K)
Carbon Region
b 1000
0.4
0.6
CO2, nf=3
CO, nf=0
CH4, nf=3
H2, nf=0
CO2, nf=0
CO, nf=3
CH4 , nf=0
4.
Concluding remarks
Acknowledgements
The authors would like to extend their thanks to UK EPSRC
for financial support under Grants EP/F027389/1. AnSteel
Group of China is acknowledged for supporting Mr T. Zhang
in the form of a visiting research fellowship. Thanks should
be given to Professor M.D. Koretsky for the constructive
discussion.
Nomenclature
AC
aji
bj
C
f
G
H
DH298
i
K
M
N
n
nf
O
P
R
RC
S
S/C
WGFR
T
V
y
m
l
b
f
7221
references
7222