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Renewable Energy
journal homepage: www.elsevier.com/locate/renene
School of Process, Environmental and Material Engineering, University of Leeds, Leeds LS2 9JT, UK
Institute of Engineering Thermophysics, Chinese Academy of Science, Beijing 100190, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 2 June 2010
Accepted 29 July 2010
Available online 23 August 2010
A detailed comparative study on thermodynamic and experimental analyses of glycerol reforming for
hydrogen production has been conducted in terms of the effects of temperature, pressure, water to
glycerol feed ratio, feeding reactants to inert gas ratio and feeding gas ow rate (residence time).
The thermodynamic analysis was conducted by using a non-stoichiometric methodology based on the
minimisation of Gibbs free energy. And the experiments were carried out with a pilot scale set-up.
The results show that the thermodynamic and experimental data agree fairly well with each other. The
measured hydrogen production is slightly lower than that predicted by the thermodynamic analysis,
which is mainly because the conversion of steam is incomplete. High temperature, low pressure, low
feeding reactants to inert gas ratio and low gas ow rate are favourable for steam reforming of glycerol
for hydrogen production. There is an optimal water to glycerol feed ratio for steam reforming of glycerol
for hydrogen production which is about 9.0. The glycerol conversion is a strong function of water to
glycerol ratio, whereas a weak function of other parameters over the conditions of this work. A novel
adsorption enhanced reaction process incorporating water and heat recovery is proposed for further
optimisation of hydrogen production from steam reforming of glycerol.
2010 Elsevier Ltd. All rights reserved.
Keywords:
Hydrogen production
Steam reforming of glycerol
Thermodynamic analysis
Experimental
Comparative study
1. Introduction
Due to the environmental concerns, the global demand for
hydrogen is expected to greatly increase in the future. One of the
solutions to this issue is to use biomass based raw materials to
produce hydrogen [1e3]. Currently, about 10 wt% of glycerol is
produced during the conversion of vegetable oils or animal fats into
biodiesel fuel through the catalytic transesterication process
[4e6]. Although a small amount of glycerol from biodiesel
production is puried for pharmaceutical and food applications, byproduct glycerol is now in surplus and the majority is taken as
a waste. This work is concerned about the use of glycerol, a major
by-product of biodiesel production, to produce hydrogen, a clean
energy carrier by steam reforming process.
A number of approaches, including aqueous phase reforming
[7], bioconversion using genetically engineered enzymes [8], auto-
(1)
780
dG
N
X
mi dni 0
(2)
i1
aji ni bj ; j 1; .; M
(3)
i1
where aji is the number of j type atoms in the i species and bj refers
to number of j type atoms in the feed. By introduction of the
Lagrangian multipliers, lj, a new function G is dened as:
N
X
i1
mi ni
M
X
j1
lj
N
X
!
aji ni bj
(4)
i1
b
DGfi =RT lnni =nT lnP ln f
i
M
X
lj aji =RT 0; i 1; .; N
j1
(5)
b is the fugacity coefcient in the gas mixture which can be
where f
obtained by the RedlicheKwong equation.DGfi is the standard Gibbs
free energy of formation which is only a function of temperature
and can be obtained from the handbooks of thermodynamic data
[24,25]. R is the universal gas constant. And nT is the total molar
number of species dened as:
nT
N
X
ni ; i 1; .; N
(6)
j1
b lc 2lo =RT 0
DGfCO2 =RT ln nCO2 =nT lnP ln f
i
(7)
b lc 2lo =RT 0
DGfCO2 =RT ln nCO2 $1 f=nT lnP ln f
i
(8)
where f is the fraction of CO2 produced in the steam-glycerol
system that is removed. Accordingly, the total molar number of
species is reduced by nCO2 $f and is expressed by:
nT
N
X
ni nCO2 $f ; i 1; .; N
(9)
i1
As the inert gas (nitrogen) was used as the carrier gas in the
experiments which is also commonly used in the experimental
studies of steam reforming of glycerol [5,6,11,14,17,20,21]. Nitrogen
is also considered in the thermodynamic analysis. Two non-linear
algebraic equations are therefore added in the chemical equilibrium system. One accounts for the atomic balance (Equation 10),
and the other for Gibbs free energy (Equation 11):
2nN2 21 WGFR=FI
b 2l =RT 0
DGfN2 =RT ln nN2 =nT ln P ln f
N
i
(10)
(11)
781
cgly
P
n_ gly;in n_ gly;out
n_ dry;out yC;out
n_ gly;in
3n_ gly;in
(12)
n_ dry;out
n_ N2 ;in
n_ N2 ;in
P
yN2 ;out
1 yi;out
(13)
where yi,out refers to the dry gas products (except for water and
nitrogen) at outlet. Due to the limit of experimental apparatus, only
four gas compositions N2, H2, CO2 and CH4 were recorded by the
ABB analyser. This assumes no other signicant dry gases than N2,
H2, CO2 and CH4 evolved from the reactor. This has been veried by
both experimental [5] and theoretical results [15] over the experimental conditions of this work. In Ref. [5] Only negligible C2H6
except for N2, H2, CO, CO2 and CH4 was detected in the experiments.
782
n_ H2 O;conv
n_ H2 O;in
(14)
H2;Sel
2n_ H2 ;out
(15)
yH
H2;pur P 2;out
yi;out
(16)
10
CH4
CO2
H2
Concentration (%)
8
6
4
2
0
500
1000
1500
2000
2500
3000
C,
P 1 bar,
6
Number of Moles
cH2 O
n_ dry;out 2yH2 4yCH4 8xgly n_ gly;in
2n_ H2 O;in
Theorectical data, H2
Theorectical data, CO2
Theorectical data, CH4
Theorectical data, CO
Measured data, H2
Measured data, CO2
Measured data, CH4
5
4
3
2
1
0
350
400
450
500
550
600
650
700
Temperature ( C)
Fig. 3. Effect of temperature: number of moles.
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
350
400
450
500
550
600
650
700
Temperature ( C)
Fig. 4. Effect of temperature: glycerol conversion, steam conversion, hydrogen selectivity and hydrogen purity.
1.0
Theorectical data, H2
Theorectical data, CO2
Theorectical data, CH4
Theorectical data, CO
Measured data, H2
Measured data, CO2
Measured data, CH4
6
Number of Moles
783
5
4
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
1
0
1
Pressure (bar)
Pressure (bar)
Fig. 5. Effect of pressure: number of moles.
784
7
6
5
Number of Moles
Theorectical data, H2
Theorectical data, CO2
Theorectical data, CH4
Theorectical data, CO
Measured data, H2
Measured data, CO2
Measured data, CH4
4
3
2
0
4
10
11
12
WGFR
Fig. 7. Effect of WGFR: number of moles.
1.0
Theorectical data, H2
Theorectical data, CO2
Theorectical data, CH4
Theorectical data, CO
Measured data, H2
Measured data, CO2
Measured data, CH4
0.9
0.8
0.7
0.6
Number of Moles
0.5
0.4
0.3
0.2
0.1
0.0
4
10
11
12
WGFR
5
4
3
2
1
0
0.250
Fig. 8. Effect of WGFR: glycerol conversion, steam conversion, hydrogen selectivity and
hydrogen purity.
0.375
0.500
0.625
0.750
785
1.0
1.0
0.9
0.9
0.8
0.8
0.7
0.7
0.6
0.5
0.6
0.4
0.5
0.3
0.4
0.2
0.3
0.1
0.2
0.0
0.250
0.1
0.500
0.625
0.750
feeding ratio
0.0
0.250
0.375
0.500
0.625
0.750
feeding ratio
Fig. 10. Effect of FI: glycerol conversion, steam conversion, hydrogen selectivity and
hydrogen purity.
Theorectical data, H2
Theorectical data, CO2
Theorectical data, CH4
Theorectical data, CO
Measured data, H2
Measured data, CO2
Measured data, CH4
7
6
Number of Moles
0.375
3
2
1
0
0.375
0.500
0.250
Fig. 12. Effect of Effect of feeding gas ow rate: glycerol conversion, steam conversion,
hydrogen selectivity and hydrogen purity.
0.625
0.750
nf
Fig. 11. Effect of feeding gas ow rate: number of moles.
786
7
6
Number of Moles
5
4
FI=1:0
FI=1:1
FI=1:2
FI=1:4
FI=1:8
FI=1:16
FI=1:32
3
2
1
0
350
400
450
500
550
600
650
700
Temperature ( C)
Fig. 15. Process with the heat regenerator.
Fig. 13. Hydrogen production at different feeding reactants: P 1 bar, WGFR 9.0.
Although the separation of water after reforming has no technical difculties, excess steam may be a hammer requiring a large
amount of water consumption and energy for heating and evaporating water. A possible methodology to tackle the problem is
shown in Fig. 15 by using a heat regenerator. In Fig. 15, the
exhausting gas is introduced into the heat regenerator, inside
which the steam is cooled and condensed and then is separated in
the liquidegas separator. Gases hydrogen and carbon dioxide are
obtained for further processing. At the same time, the liquid water
is recycled and pumped back through the heat regenerator to
extract the heat from exhausting gas and then is injected and mixed
with feeding glycerol for reforming reaction. One can see that the
process in Fig. 15 combines the heat regeneration and water
separation within one heat regenerator.
It should be noticed that although the increase in feeding steam
ratio would increase the production of hydrogen, this effect
becomes limited at high feeding steam ratio, especially at higher
temperature [30]. Additionally, the regenerator could be very big
comparing with the reactor and may be not so cost effective for the
steam reforming process at very high feeding steam ratio conditions. Further work is obviously needed for optimising the process
in Fig. 15.
H2, FI=1:0
CH4, FI=1:0
CO, FI=1:0
CO2, FI=1:0
7
6
5
4
FI=1:0 (WGFR=9:1)
FI=1:1 (WGFR=19:1)
FI=1:2 (WGFR=29:1)
FI=1:4 (WGFR=49:1)
FI=1:8 (WGFR=89:1)
FI=1:16(WGFR=169:1)
FI=1:32(WGFR=329:1)
3
2
1
400
450
500
550
600
650
700
Molar number
Number of Moles
0
350
H2, FI=1:4
CH4, FI=1:4
CO, FI=1:4
CO2, FI=1:4
5
4
3
2
1
0
0.0
0.2
0.4
0.6
CO2 removal fraction
0.8
1.0
Temperature ( C)
Fig. 14. Hydrogen production at different feeding steam ratio: P 1 bar.
f
G
H
DH298
i
K
M
N
n
nf
O
P
R
RC
S
S/C
WGFR
T
V
y
Fig. 17. Process with CO2 adsorption.
6. Conclusions
A detailed comparative study on thermodynamic and pilot-scale
experimental analyses of glycerol reforming for hydrogen production has been conducted in terms of temperature, pressure, water
to glycerol feed ratio, feeding reactants to inert gas ratio and
feeding gas ow rate (residence time). Following conclusions can
be drawn:
(1) Thermodynamic and experimental data agree fairly well with
each other and they have same trend in terms of all the 5
parameters. But the measured hydrogen production is slightly
lower than that predicted by the thermodynamic analysis. The
major reason lies in the conversion of steam is incomplete.
(2) High temperatures, low pressure, low feeding reactants to inert
gas ratio and low gas ow rate are favourable for steam
reforming of glycerol for hydrogen production. However, there
is an optimal water to glycerol feed ratio for steam reforming of
glycerol for hydrogen production which is about 9.0. The
glycerol conversion is a strong function of water to glycerol
ratio, but a weak function of other parameters over the
conditions of this work.
(3) Methodologies for further optimisation of the steam reforming
of glycerol for hydrogen production have been discussed
including a lower feeding reactants to inert gas ratio, a higher
water to glycerol feed ratio and carbon dioxide removal. A new
adsorption enhanced reaction process incorporating water and
heat recovery is proposed which clearly requires further
investigation.
Acknowledgement
The authors would like to extend their thanks to UK EPSRC for
nancial support under Grant EP/F027389/1.
Nomenclature
AC
aji
bj
C
m
l
b
f
787
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