i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

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Comparison of several glycerol reforming methods

for hydrogen and syngas production using Gibbs
energy minimization

Antonio C.D. Freitas, Reginaldo Guirardello*

School of Chemical Engineering, University of Campinas (UNICAMP), Av. Albert Einstein 500, 13083-852 Campinas,
SP, Brazil

article info abstract

Article history: This paper focuses on the comparison of different glycerol reforming technologies aimed
Received 12 December 2013 to hydrogen and syngas production. The reactions of steam reforming, partial oxidation,
Received in revised form autothermal reforming, dry reforming and supercritical water gasification were analyzed.
26 February 2014 For this, the Gibbs energy minimization approach was used in combination with the virial
Accepted 18 March 2014 equation of state. The validation of the model was made between the simulations of the
Available online 13 April 2014 proposed model and both, simulated and experimental data obtained in the literature. The
effects of modifications in the operational temperature, operational pressure and reactants
Keywords: composition were analyzed with regard to composition of the products. The effect of coke
Reforming processes formation was discussed too. Generally, higher temperatures and lower pressures resulted
Gibbs energy minimization in higher hydrogen and syngas production. All reforming technologies demonstrated to be
Hydrogen feasible for use in hydrogen or synthesis gas production in respect of the products
Syngas composition. The proposed model showed good predictive ability and low computational
time (close to 1 s) to perform the calculation of the combined chemical and phase equi-
librium for all systems analyzed.
Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Glycerol is obtained as a by-product in biodiesel production

Introduction
In the past decades, biomass has received a great deal of
attention as a new source for clean energy because it is
renewable, alternative and producing less carbon dioxide
than fossil fuels [1]. In the last decade, biodiesel has been
becoming a major substitute for fossil diesel, as its environ-
mental benign characteristics can reduce carbon dioxide
emission pollution and mitigate climate change problems
[2,3].
using vegetable oils by a base-catalyzed transesterification
reaction. Glycerol of high purity is an important industrial
feedstock for applications in food, cosmetics, pharmaceutical
and other industries [4]; however, it is costly to refine crude
glycerol, especially for medium and small-sized plants.
In any case, since glycerol production and utilization have
a notable impact on the economics and sustainability of bio-
diesel production, the development of novel processes for
glycerol valorization is essential. Among all possible routes,
glycerol conversion into valuable gases like as hydrogen and

* Corresponding author. Tel.: þ55 19 3521 3955; fax: þ55 19 3521 3910.
E-mail addresses: guira@feq.unicamp.br, guira@pq.cnpq.br (R. Guirardello).
http://dx.doi.org/10.1016/j.ijhydene.2014.03.130
0360-3199/Copyright ª 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
17970 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

syngas as an energy carrier using different reforming pro- the hydrogen available on the market. In this process the
cesses are one of the most attractive ways to aggregate value substrate is reacted with steam in the presence of a catalyst to
in the glycerol [4]. produce hydrogen or syngas.
The reforming processes used to produce hydrogen and The SR is an endothermic process, i.e. energy is needed for
syngas from glycerol include some methods, and in the liter- this process. This energy is used to break up the CeC and HeC
ature, it is possible to find some articles about then. The ar- bonds in the chain of the reactant. The high-energy con-
ticles principally discussing the catalytic behavior of the sumption in the steam reforming process is the principal
systems, the main related methods for glycerol reforming are drawback of this process.
steam reforming (SR) [5e11], partial oxidation (or oxidative The principal advantages of the SR are that it can convert
reforming) (PO) [12e14], autothermal reforming (ATR) [12,14] the substrate in hydrogen at low pressures and can produce
and supercritical water gasification (SCWG) [15e19]. high concentrations of hydrogen with high substrate conver-
Other methods like as dry reforming (or CO2 reforming) sions when compared with other reforming process [26].
(DR) [20,21], dry autothermal (a combination between dry, Many papers have been performed on hydrogen produc-
oxidative and steam reforming) [22] and pyrolysis [23], also, tion from hydrocarbons and biomass materials using SR pro-
were evaluated as possible routes for glycerol conversion. cesses, like as Adhikari et al. [7,24,27,28], Slinn et al. [29],
Normally catalysts were used to promote and accelerate Oliveira et al. [30] and Rass-Hansen et al. [26]. Different au-
these reforming processes. Ni, Co and noble metals like as Pt, thors evaluated the SR of glycerol in the last years
Pd and Rh based catalysts were related to promote the [8,10,31e36], most of these works talk about the catalytic
reforming process. Among then, the Ni based catalysts are the behavior and about the effects of different catalysts in SR
most commonly used. The main reactions that can be systems. The conditions related to be the more favorable to
occurred in the reforming processes of glycerol are presented reforming reactions are 500e900  C, 1 atm and 6-9/1 of water/
in Table 1. glycerol molar ratio.
In the following sections, the steam, oxidative, auto-
thermal, dry and supercritical water reforming reactions will Partial oxidation of glycerol (PO)
be discussed, in terms of reactions conditions and character-
istics of the reactions for hydrogen and syngas production. In the PO the substrate is reacted with oxygen or air. The re-
action results in great amounts of energy and high tempera-
Steam reforming of glycerol (SR) tures are observed, temperatures close to 1000  C are reported
in the literature [37]. As a result, no external heat is required to
SR is the most commonly used technology for producing drive the reactions in a PO process once the reaction is
hydrogen in the chemical industry especially from methane initiated.
[24,25]. The SR of natural gas produces approximately 90% of This reaction may be conducted with or without catalysts
and the production of syngas is favored because the carbon
monoxide (CO) selectivity is higher in the PO process when
compared with the SR process [37].
Table 1 e Main reactions in glycerol reforming processes.
Although the PO process presents low energy requirements
Reaction DHR298 K ðkJ$mol1 Þ than SR it commonly operates at very high temperature in
Glycerol oxidation reactions non-catalytic process (above 1200  C). In the last decade, some
C3H8O3 þ 0.5O2 / 2CO þ CO2 þ 4H2 32 (1) studies analyzed the catalytic PO promoted by different
C3H8O3 þ 3.5O2 / 3CO2 þ 4H2O 1565
metallic catalysts. Ni, Pt and Rh based catalysts are the most
C3H8O3 þ 1.5O2 / 3CO2 þ 4H2 598
commonly used in the PO reaction. Normally was observed
Steam reforming of glycerol/SCWG
C3H8O3 þ 3H2O 4 3CO2 þ 7H2 128 (2) that in the catalytic PO high conversions are achieved and
Glycerol decomposition equilibrium compositions are observed in temperatures above
C3H8O3 4 4H2 þ 3CO 250 (3) 600  C [38,39].
Water gas shift reaction
CO þ H2O 4 CO2 þ H2 41 (4) Autothermal reforming of glycerol (ATR)
CO disproportionation reaction
2CO 4 CO2 þ C(s) 172 (5)
Methanation of CO (6)
The ATR of glycerol is a combination of SR and PO. ATR, as
CO þ 3H2 4 CH4 þ H2O 206 well as PO, does not require an additional heat supply once the
Methanation of CO2 reaction is initiated. Thus, ATR can be run up automatically by
CO2 þ 4H2 4 CH4 þ 2H2O 165 properly adjusting the reactive conditions [37e40]. Addition-
Methane steam reforming ally the reactor temperature can be optimized and the catalyst
CH4 þ H2O 4 3H2 þ CO 207 (7)
deactivation can be avoided by manipulation of the reactants
Methane dry reforming
compositions in the ATR [41].
CO2 þ CH4 4 2H2 þ 2CO 247 (8)
Methane decomposition The main advantages of the ATR are that lower energy is
CH4 4 2H2 þ C(s) 76 (9) supplied than in steam reforming and the composition of the
Methane oxidative reforming products out-stream can be easily manipulated by modifica-
CH4 þ 0.5O2 4 2H2 þ CO 38 (10) tion in the inlet-stream.
Carbon gasification Different studies analyzed the ATR of glycerol experi-
C(s) þ 2H2O 4 2H2 þ CO2 90 (11)
mentally Dauenhauer et al. [42] and Douette et al. [43]
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4 17971

evaluated the behavior of the ATR of glycerol in the presence energy minimization approach in combination with the virial
of Pt and Ni based catalysts respectively. Conversions close to EoS. Comparisons between experimental and simulated data
equilibrium ones are reported by the authors. obtained from literature for these systems were performed. In
addition, the effects of the process variables (temperature,
Dry reforming of glycerol (DR) pressure and inlet composition) were evaluated with respect
to the product compositions. The effects of the presence of
The DR process for syngas production has attracted much catalysts in the system and formation of coke were discussed
attention from both industrial and environmental aspect. too.
Glycerol reforming with CO2 could be an attractive process
mainly because of the biodiesel-derived glycerol is considered
renewable and the CO2 will be converted in syngas or high Methodology
value added gases.
However the coke (C(s)) formation in the DR is more severe Model formulation
than in other reforming process, due to the lower H/C ratio of
this reaction [44]. One of the obstacles encountered in the Gibbs energy minimization model
application of this technology is the rapid deactivation of the The thermodynamic equilibrium condition for reactive
catalyst, which is mainly due to coke accumulation and multicomponent closed system, at constant pressure and
sintering of both the support and the active metal particles temperature, with given initial composition, can be obtained
[20]. by the minimization of Gibbs energy (G) of the system, with
No papers evaluating the experimental behavior of the DR respect of the number of moles of each component in each
of glycerol were found in the literature. Wang et al. [20] per- phase, given by:
formed the thermodynamic analysis of glycerol dry reforming
using the Lagrange’s undetermined method in Matlab soft- X
NC
g g
X
NC X
NC
minG ¼ ni mi þ nli mli þ nsi msi (12)
ware. The authors observed that higher pressures have a i¼1 i¼1 i¼1
negative effect on both hydrogen and syngas yield, the
While satisfying the restrictions of non-negative number of
hydrogen yield increases with increasing temperature and
moles of each component in each phase:
large amounts of CO2 in the feed results in poor hydrogen
generation. g
ni ; nli ; nsi  0 (13)

Supercritical water gasification of glycerol (SCWG) In addition, the restriction of mole balances, given by atom
balance for reactive systems (non-stoichiometric
The SCWG reaction occurs in an aqueous fluid phase under formulation):
conditions that exceed the critical point of water
P
NC  g  P
NC
(TC ¼ 647.15 K, PC ¼ 21.9 MPa). Supercritical water has unique ami $ ni þ nli þ nsi ¼ ami $n0i m ¼ 1; .; NE (14)
i¼1 i¼1
features with respect to its density, dielectric constant, ion
product, viscosity, diffusivity, electric conductance and sol- Smith and Missen [53] demonstrated that the stoichio-
vent ability [45]. metric formulation is equivalent to the non-stoichiometric
SCWG of biomass seems to be a promising technology for one, if all independent reactions are considered.
g
the production of hydrogen and other useful gases from wet The values of mi can be calculated from the formation
biomass [46]. The main advantage of the SCWG are that the values given at some reference conditions, using the following
process does not require the expensive drying process, thermodynamic conditions:
necessary for others thermochemical process for trans-
vHi 
formation of biomass [47e49]. However high-energy costs are ¼ Cpi i ¼ 1; .; NC (15)
vT P
associated with the compression steps.
Other important factor in SCWG is that high temperature v  mi  Hi
and pressures of the process ensure that intrinsic reaction ¼ i ¼ 1; .; NC (16)
vT RT P R$T2
rates are high, and near equilibrium conversions being
In this work, which considers only a gas phase and a
reached [50]. It is generally believed that the ionic product and
possible solid phase as carbon for coke formation, the Gibbs
dielectric constant of water below its critical point are the
energy can be expressed as:
major factors controlling hydrolysis reactions of organic ma-
terials [51]. X  X
g 
NC NC

May et al. [52] and Byrd et al. [15] evaluated the SCWG of G¼ ni m0i þ RT ln P þ ln yi þ ln 4i þ nsCðsÞ m0CðsÞ (17)
i¼1 i¼1
glycerol in a catalytic system. The authors observed that
glycerol was completely gasified to hydrogen, carbon dioxide Since, some of the systems analyzed by the present work
and methane with only small amounts of carbon monoxide was at high pressure, the virial equations of state (EoS) trun-
and the hydrogen yield were found to increase directly with cated at second virial coefficient, were utilized to determine
temperature. the fugacity coefficient. The second virial coefficient was
In this paper, we focused on the comparison of several calculated by the correlation of Pitzer and Curl [54], which was
glycerol reforming technologies. The SR, PO, ATR, DR and modified by Tsonopoulos [55]. The following relation deter-
SCWG of glycerol were analyzed. For this, we used the Gibbs mined the fugacity coefficient:
17972 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

2 3
X
m
P Table 2 e Chemical compounds considered in the
b i ¼ 42
ln f yj Bij  B5 (18)
j
RT simulations and your thermodynamic properties.
Compound Chemical TC PC VC u ()a
The Gibbs energy minimization method is widely a a 3
formula (K) (bar) (m /kmol)a

studied in the literature, being applied in a wide range of

Water H2O 647.3 220.0 0.056 0.348
systems [12,13,20,24,28,56e64]. Some of then related to glyc- Glycerol C3H8O3 850.0 75.0 0.260 0.513
erol reforming processes [13,20,24,28,56], but none of them Hydrogen H2 33.0 13.0 0.064 0.000
presents a complete thermodynamic study about these Methane CH4 191.1 45.8 0.099 0.013
reactions. Carbon dioxide CO2 304.2 73.9 0.094 0.420
Carbon monoxide CO 133.0 35.0 0.093 0.041
Oxygen O2 154.6 50.4 0.073 0.022
Model implementation Ethane C2H6 305.4 48.2 0.148 0.105
Propane C3H8 369.9 42.0 0.200 0.152
During the process of optimization, utilizing the Gibbs energy Ethylene C2H4 283.1 50.5 0.124 0.073
g Propylene C3H6 369.9 45.4 0.182 0.143
minimization method the number of moles of the gaseous (ni )
Methanol CH3OH 512.6 80.1 0.116 0.559
and solid (nsi ) phase are considered decision variables, while T,
Ethanol C2H5OH 514.0 61.4 0.168 0.644
P and the chemical potential of the pure component in the Acetone C3H6O 508.1 47.0 0.209 0.304
reference state (m0i ) are considered parameters. Acetaldehyde C2H4O 461.0 55.7 0.154 0.303
The software GAMS 23.2.1, (General Algebraic Modeling a
Source: Refs. [66e68].
System) with the CONOPT solver was used in the resolution of
the combined chemical and phase equilibrium problem.
A description of GAMS software can be found in Brooke
et al. [65]. The solid phase formed was considered as solid Model validation
carbon (pure component). These methodologies and consid-
erations were applied in previous works in literature with The validation was performed using simulated and experi-
good predictive results for similar systems with methane and mental data obtained in literature in comparison with the
biomass [58e62]. simulations performed using the proposed virial model. The
A total of 15 output compounds were selected as repre- objective of the validating the model is to verify the predictive
sentative of the main compounds, which can be found in the ability of the model against experimental data obtained in the
output stream of these reactive systems. The thermodynamic literature and verify the ability of the virial equation in
data used in the calculations were obtained from literature represent the non-ideality’s of the studied systems.
[66e68]. In order to compare the results calculated using the pro-
In almost all the thermodynamic analyses of glycerol posed approach with the values found in literature, the mean
reforming processes, the systems were represented consid- relative error (MRE) was used, according to equation (19).
ering primary species, such as hydrogen, methane, carbon  
X NCE xlit  xsim 
NPE X
monoxide, carbon dioxide, water and glycerol, and in some 1  j;i j;i 
MRE ¼ $   (19)
NPE$NCE j  xlit 
papers the solid carbon (C(s)) was considered too. The i j;i

consideration of the formation of solid carbon is very impor-

tant because the C(s) can poison the catalyst in reforming re-
actions [44].
However, some experimental works in the literature
related the presences of secondary components in these re-
actions, some of the secondary compounds are methanol,
ethanol, acetaldehyde, acetone and ethane [23,69]. In this
work, a complete thermodynamic analysis of these reactions
was performed and all species mentioned above and some
others have been take into account.
The complete list of output compounds, along with their
critical parameters, is reported in Table 2.
Results and discussion
Production of hydrogen and syngas has been analyzed in
different pressure, temperature and inlet composition condi-
tions in the SR, PO, ATR, DR and SCWG from glycerol. In the
following section, the proposed model was validated with
simulated and experimental data obtained in the literature for
the different glycerol reforming technologies evaluated by the
present work.
where NPE is the number of experimental points, NCE is the
number of components for each experimental point, xsim j;i is
the value calculated by the present work using the proposed
virial model and xlitj;i is the experimental or simulated value
obtained in the literature.
Fig. 1 shows the validation of the virial proposed model in
comparison with the experimental results of Byrd et al. [15]
and the simulated results from the work of Castello and
Fiori [56]. The experiments of Byrd et al. [15] were performed at
the following conditions: temperature of 800  C (1073.15 K),
pressure of 241 bar and with feed concentration in the range of
5e40 wt%.
The simulations of the present work and that obtained in
the work of Castello and Fiori [56] were performed under the
same above-mentioned conditions. However, Castello and
Fiori [56] used the PengeRobinson EoS in the Gibbs energy
minimization model.
Analyzing Fig. 1 it is possible to verify that the virial pro-
posed model predictions are in good agreement with the
experimental behavior reported by Byrd et al. [15]. The highest
deviations were observed in the higher initial feed concen-
tration region (above 25 wt%). It can also be seen that the
model predictions for H2 production is better than that
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4
Fig. 1 e Virial model validation with the experimental data
from Byrd et al. [15] and the simulated data from Castello
and Fiori [56] for the SCWG of glycerol. Symbols: solid line:
virial proposed model predictions; black symbols:
experimental data from Byrd et al. [15]; dashed
line D white symbols: simulated data from Castello and
Fiori [56].
observed for the other compounds (CO2, CH4 and CO). The
MRE between the experimental and simulated data was 0.692.
Still in Fig. 1, it is also interesting to note that the use of the
virial equation instead of PengeRobinson EoS does not result
in changes in the predictive ability of the Gibbs energy model,
although it leads to a significant mathematical simplification
of the Gibbs energy minimization problem.
The experimental results for the H2 yield were obtained in
the work of Byrd et al. [15] too. The simulations were per-
formed at the same above-mentioned conditions and the
comparison is presented in Fig. 2(a).
It is interesting to emphasize that the model predictions for
the H2 yield were good. The MRE between the experimental
and simulated data was 0.104. Analyzing Fig. 2(a) it is possible
to verify that increasing the concentration of glycerol in the
feed is associated with decrease in the hydrogen concentra-
tion and an accompanying increase in the methane concen-
tration in the product. This trend can be explained by
considering that less water is present at the higher concen-
trations of glycerol in the feed.
In Fig. 2(b) the effect of modifications in the reaction tem-
perature was analyzed, the simulations were performed at the
following conditions: pressure of 241 bar; residence time of 1 s
and with 5 wt% of glycerol in the feed stream. The observed
MRE was low: 0.44 indicating good ability of the model to
predict the effect of reaction temperature.
Analyzing Fig. 2(b) it’s possible to verify that the elevation
of the reaction temperature resulted in improved prediction
capability of the model in comparison with the behavior of the
experimental data. It can also be seen that the methane
composition is slightly higher at lower temperatures, and this
trend was well represented by the model predictions.
Analyzing Figs. 1 and 2(a) and (b) it’s possible to see that the
experimental gas compositions and H2 yields closely mirror
the equilibrium compositions calculated by the proposed
virial model, this behavior indicate that the reaction is near its
17973
Fig. 2 e Comparison between experimental data from Byrd
et al. [15] and the results obtained using the proposed virial
model for (a) H2 yield for the SCWG of glycerol; (b) product
gas composition as function of reaction temperature.
thermodynamic equilibrium. For higher glycerol concentra-
tion in the feed, was observed that the experimental carbon
monoxide concentrations are smaller than predicted by the
thermodynamic model, the behavior for H2 and CO was the
opposite, and the experimental data was higher than pre-
dicted by the thermodynamic model. This behavior can be
explained by the water gas shift reaction (Eq. 4, in Table 1), it is
possible that this reaction has not reached the equilibrium
condition in the experimental conditions.
In Fig. 3, the validation of the virial model is performed
with the simulated and experimental data obtained in the
work of Wang et al. [70] for the steam reforming of glycerol.
The experiments of the Wang et al. [70] were performed at
923 K, in the presence of Ni/ZrO2 catalyst and with two
different water to glycerol molar ratios in the feed, 6 and
9. Fig. 3(a) presents the results obtained to a WGR of 6 and
Fig. 3(b) the results to a WGR of 9.
The simulations performed using the proposed virial
model and the simulations obtained in the work of Wang et al.
[70] were performed in the same aforementioned experi-
mental conditions. The simulations of Wang and coworkers
were performed using the ideal gas formulation and the
Lagrange’s undetermined multiplier method.
Analyzing Fig. 3 is possible to verify that the description of
the experimental data is better for the simulations performed
17974 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

Fig. 3 e Comparison of product composition (dry basis) between experimental and simulated data from Wang et al. [70] and
the predictions obtained using the virial proposed model for the steam reforming of glycerol with different WGR in the feed
(a) WGR-6; (b) WGR-9.

by the present work, using the virial model, than the simu-
lations of Wang et al. [70] that used the consideration of
ideality.
The product compositions are close to the thermody-
namic equilibrium values over the investigated reaction
conditions. The MRE between the experimental and simu-
lated data was 0.232 for the WGR of 6 and was 0.310 for the
WGR of 9.
Douette et al. [43] studied the autothermal reforming of
glycerol using a 23 factorial experimental design, in a fixed be
reactor of nickel based catalyst. The effects of the oxygen to
carbon ratio, steam to carbon ratio and reformer temperature
were evaluated over H2 yield, CO yield and CO2 yield. Table 3
presents the experimental conditions of the 12 experiments
performed by Douette and coworkers, all experiments were
conducted at atmospheric pressure.
The experimental results obtained by Douette et al. [43] for
the conditions presented in Table 3 and the predictions ob-
tained by the present work using the virial model can be
visualized in Fig. 4(a)e(c) for the H2 yield, CO yield and CO2
yield, respectively, as a function of the conditions presented in
Table 3.

Table 3 e Experimental conditions in the work of Douette

et al. [43] for the autothermal reforming of glycerol.
Condition Variable values
number
Oxygen to Steam to Temperature (K)
carbon ratio carbon ratio
1 0.40 2.00 1043.15
2 0.70 2.00 1043.15
3 0.40 2.70 1043.15
4 0.70 2.70 1043.15
5 0.40 2.00 1123.15
6 0.70 2.00 1123.15
7 0.40 2.70 1123.15
8 0.70 2.70 1123.15 Fig. 4 e Comparison between experimental results of
9 0.55 2.40 1083.15 Douette et al. [43] and the predictions obtained using the
10 0.55 2.40 1083.15 virial model for the autothermal reforming of glycerol for
11 0.30 2.30 1080.15 the (a) gas yield of H2; (b) gas yield of CO; and (c) gas yield of
12 0.00 2.20 1077.15
CO2.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4
Fig. 5 e Comparison between simulated data of Wang et al.
[20] and the simulations performed by the present work
using the virial proposed model for the dry reforming of
glycerol. Symbols: solid line: syngas production; dashed
line: hydrogen production; black symbols: simulated data
from Wang et al. [20] for syngas production; white
symbols: simulated data from Wang et al. [20] for hydrogen
production.
The MRE between the experimental and simulated data
was 0.292 for H2 yield (Fig. 4(a)), 0.054 for CO yield (Fig. 4(b)) and
0.039 for CO2 yield (Fig. 4(c)).
The highest deviations were observed for H2 (Fig. 4(a)),
especially in conditions 2, 6, 8, 9, 10 and 12. No direct rela-
tionship was observed to relate the points with larger de-
viations, however, we point out that for many of these cases
large deviations were observed as the experimental data is for
the composition of CO2, CO and H2. These deviations may be
associated with larger deviations in conditions 2, 6, 8, 9, 10 and
12.
Wang et al. [20] performed the thermodynamic analysis of
the dry reforming of glycerol using the Gibbs energy minimi-
zation in the Matlab language. The Lagrange undetermined
multiplier method and the ideal gas consideration are used.
Fig. 5 presents the comparison between the simulated data
obtained in the work of Wang et al. [20] and the simulations
performed using the virial proposed model for the DR of
glycerol.
The simulations performed by the present work are in
excellent agreement with the simulations obtained in the
work of Wang et al. [20]. The MRE between the data was 0.063
for the number of moles of H2 and 0.058 for the number of
moles of syngas. No experimental data was obtained in the
Table 4 e Conditions evaluated in the different glycerol reforming processes evaluated.
Reforming technology Reaction temperature
range (K)
Steam reforming (SR) 773.15e1273.15
Partial oxidation (PO) 773.15e1273.15
Autothermal reforming (ATR) 773.15e1273.15
Dry reforming (DR) 773.15e1273.15
Supercritical water gasification (SCWG) 773.15e1273.15
17975
literature for this system, thus the comparison with experi-
mental data was not possible for DR of glycerol.
With the results was possible to verify that the proposed
model has good predictive ability, and can therefore be used to
predict the thermodynamic behavior of the different reform-
ing technologies of glycerol evaluated by the present work. In
the following sections, the model was used to study different
reforming technologies of glycerol for hydrogen and syngas
production, evaluating the effect of modification in the oper-
ational temperature, pressure and in the reactants
composition.
Hydrogen and syngas production
In the following sections, the results obtained using the virial
model for different glycerol reforming technologies are pre-
sented. For each reaction a detailed thermodynamic evalua-
tion is presented, based on thermodynamic effects of
temperature, pressure and reactant composition. The condi-
tions under each one of the glycerol reforming technologies
were evaluated are presented in Table 4, and the effect of each
one of these variables is evaluated under the production of H2
and syngas.
Steam reforming
Fig. 6 shows the results obtained using the Gibbs energy
minimization combined with virial model for the effects of
temperature (Fig. 6(a)), pressure (Fig. 6(b)) and glycerol/water
molar ratio (Fig. 6(c)) in the SR of glycerol.
The effect of changes on operating temperature, at atmo-
spheric pressure, on the equilibrium compositions under H2,
CO and syngas production are show in Fig. 6(a). The glycerol/
water molar ratio was set at 1/3. The elevation of the operating
temperature results in the increased productions of H2 and CO
until the temperature of 1173.15 K. Above this temperature the
elevation of operating temperature did not result in increases
in H2, CO, and consequently syngas, production. Similar
behavior was observed in the simulations performed by
Adhikari et al. [24]. This behavior can be explained by the
occurrence of reverse water gas shift reaction (Eq. (4) in Table
1) in conditions of high temperature.
Fig. 6(b) shows the effect of pressure under H2, CO and
syngas production. The temperature and the glycerol/water
molar ratio were fixed in 973.15 K and 1/3, respectively.
The elevation of the pressure results in decreased pro-
duction of the interest products, this effect was observed in all
range of pressure analyzed (1e20 bar). For example, the in-
crease in the pressure of 1e20 bar results in a decrease of 58%
Reaction pressure Feed composition range
range (bar)
1e20 bar 1/0.5e3.0 glycerol/H2O molar ratio
1e20 bar 1.0/0.25e1.5 glycerol/O2 molar ratio
1e20 bar 1/0.5e1.5/0.0e1.5 glycerol/H2O/O2 molar ratio
1e20 bar 1/0.5e3.0 glycerol/CO2 molar ratio
250e350 bar 10e35 wt% of glycerol
17976 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4
Fig. 6 e Hydrogen, carbon monoxide and syngas molar
composition in the dry gas for steam reforming of glycerol
as function of (a) temperature; (b) pressure and (c) glycerol/
water molar ratio.
of the number of moles of H2 and of 60% of the number of
moles of syngas produced in the SR system.
The effect of modification in the glycerol/water molar ratio
with respect to H2, CO and syngas production is presented
in Fig. 6(c). The pressure and the temperature were set at 1 bar
and 973.15 K, respectively. It is interesting to verify that higher
amounts of H2O in the feed results in higher concentration of
H2 in the product. Already CO formation decreases with higher
amounts of H2O in the feed.
The increase in the H2O molar ratio in the feed of 0.5e3.0
resulted in a 43% of increase in the number of moles of H2 in
the product stream. The H2/CO molar ratio obtained as func-
tion of the glycerol/water molar ratio is presented in Fig. 7. The
conditions used in the simulations were the same used
in Fig. 6(c) (973.15 K and 1 bar). H2/CO molar ratio of 2.0 (ideal
for FischereTropsch applications) was obtained with a glyc-
erol/water molar ratio of 1.0/1.5 in the feed.
Fig. 7 e H2/CO molar ratio for the steam reforming of
glycerol as function of glycerol/water molar ratio in the
feed. Simulation conditions: pressure: 1 bar; temperature:
973.15 K.
The increase of the H2O concentration in the feed results in
increased production of H2 and consequently in the elevation
of the H2/CO molar ratio, for example, the H2/CO molar ratio
was 1.99 for the 1.0/1.5 glycerol/water molar ratio and 2.68 in
the 1.0/3.0 glycerol/water molar ratio. Under the conditions
evaluated was not observed significant formation of solid
carbon in the steam reforming of glycerol.
In SR of glycerol was observed the formation of H2, CO, CO2,
CH4, unreacted H2O and small amounts of C2H6. At lower
temperatures, below 973.15 K, the main compound in the
output stream are H2 and CO2. With increasing temperature
(above 973.15 K), the main compounds become H2 and CO.
Solid carbon formation was observed at conditions of low H2O
molar ratios in the feed and at low temperatures (below
873.15 K).
Partial oxidation
The PO of glycerol were thermodynamic evaluated using the
proposed virial model, and Fig. 8 shows the results obtained.
Fig. 8(a) presents the effect of modification in operating tem-
perature, Fig. 8(b) presents the effect of pressure and Fig. 8(c)
presents the effect of glycerol/O2 molar ratio.
For evaluate the effect of the operating temperature, the
pressure and the glycerol/O2 molar ratio in the feed were set at
1 bar and 1.0/0.5, respectively. The elevation of operating
temperature results in both, elevation of H2 and CO produc-
tion, and consequently syngas production (see Fig. 8(a)). This
effect was observed until the temperature of 1173.15 K, above
this temperature the production of CO and H2 decreased.
The effect of the pressure under H2 and CO formation is
show in Fig. 8(b). The simulations were performed at constant
temperature and glycerol/O2 molar ratio of 973.15 K and 1.0/
0.5. The elevation of the operation pressure results in reduced
production of H2 and CO. The same effect was observed in the
steam reforming of glycerol.
Fig. 8(c) depicts the effect of modifications in the glycerol/
O2 molar ratio under the production of H2, CO and syngas. The
simulations were performed at constant temperature and
pressure of 973.15 K and 1 bar. It is interesting to verify that
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4
Fig. 8 e Hydrogen, carbon monoxide and syngas molar
composition in the dry gas for partial oxidation of glycerol
as function of (a) temperature; (b) pressure and (c) glycerol/
water molar ratio.
the elevation of O2 ratio in the feed results in reduced pro-
ductions of H2 and CO. Higher amounts of CO2 and H2O were
observed in that conditions. For example, raising the glycerol/
O2 molar ratio of 1.0/0.25 to 1.0/1.50 resulted in a 26% decrease
in the number of moles of H2 and 38% in the number of moles
of CO in the system; however, the variation of the molar
fraction is small.
The PO of glycerol presented significant C(s) formation
under the conditions in which the reaction was analyzed by
the present work. Thus, Fig. 9 presents the formation of solid
carbon as function of the operating temperature (Fig. 9(a)) and
pressure (Fig. 9(b)).
The simulations conducted to evaluate the temperature
effect were performed at constant pressure (1 bar) and
the simulations performed to evaluate the pressure effect
were performed at constant temperature (973.15 K) in
both cases the glycerol/O2 molar ratio was kept constant
(1.0/0.5).
17977
Fig. 9 e Solid carbon formation in the partial oxidation of
glycerol as function of temperature (a) and pressure (b).
Analyzing Fig. 9(a) it is possible to verify that the elevation
of the process temperature results in significant reductions in
C(s) formation and at 973.15 K the C(s) formation has been
eliminated by thermodynamic effects.
Fig. 9(b) presents the effect of the pressure over the C(s)
production. The elevation of the pressure results in an in-
crease in the C(s) formation. At 1 bar no C(s) formation was
observed. The coke formation showed a linear increase with
increasing of the operating pressure of the system throughout
the pressure range examined.
In the PO of glycerol was observed the formation of H2, CO,
CO2, CH4, and small amounts of C2H6 and C2H4 at low tem-
perature conditions (below 93.15 K). The O2 and the glycerol
were completely converted, the formation of solid carbon was
observed in the PO mainly because the reaction was con-
ducted at low O2 concentrations in the feed, to avoid the
occurrence of the complete combustion reaction. However, at
some interesting conditions for H2 and syngas production the
formation of solid carbon was not observed, even using low
concentrations of O2.
Autothermal reforming
Fig. 10(a) shows the effect of the temperature in respect of H2
and CO formation in the ATR of glycerol. The simulations were
performed at constant pressure and glycerol/H2O/O2 molar
ratio of 1 bar and 1.0/1.0/1.0 respectively.
As observed in the reactions previously showed (SR and PO),
the formation of the interest products increased with
increasing in temperature for CO in the whole range of tem-
perature examined. Increasing in the H2 production was
17978 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4
Fig. 10 e Hydrogen, carbon monoxide and syngas molar
composition in the dry gas for autothermal reforming of
glycerol as function of (a) temperature; (b) pressure and (c)
glycerol/H2O/O2 molar ratio.
observed until 973.15 K, above this temperature the number of
moles of H2 produced decrease with increasing the
temperature.
Fig. 10(b) presents the behavior of formation of H2 and CO
as function of the pressure of the system. The simulations
were performed at constant pressure and glycerol/H2O/O2
molar ratio, of 973.15 K and 1.0/1.0/1.0 respectively. It is
interesting to emphasize that the elevation of the pressure
results in decreased formation of interest products.
Fig. 10(c) depicts the results obtained by the simulations for
different glycerol/H2O/O2 molar ratios at constant pressure
(1 bar) and temperature (973.15 K). First, the molar ratio of H2O
was set at 0.5 and the molar ratio of O2 varied between 0.0 and
1.5. Under these conditions, it is interesting to emphasize that
the molar fractions of H2 and CO decreased with the addition
of O2. Secondly, the molar ratio of O2 was set at 0.5 and the
molar ratio of H2O varied between 0.0 and 2.0. It is interesting
to verify that the number of moles of H2 significantly increases
with H2O addition and the production of CO decreases at the
same conditions.
Fig. 11 shows the behavior of the H2/CO molar ratio as a
function of the glycerol/H2O/O2 molar ratio. For these simu-
lations the pressure and the temperature was kept constant in
1 bar and 973.15 K. It is interesting to emphasize that the
addition of water, with a constant molar ratio of O2 (of 0.5),
results in an increase in the H2/CO molar ratio. Molar ratios
close to two are achieved with a glycerol/H2O/O2 molar ratio of
1.0/1.5/0.5.
Another interesting effect is that the composition of the
products stream can be easily modified by changes in the feed
composition the amount of O2 is a key issue in the ATR pro-
cess because it can strongly affect the H2 production in this
process.
No C(s) formation was observed in the conditions analyzed
for this reforming technology. Significant amounts of H2 and
CO were produced at high temperature conditions. The for-
mation of C2H6 was also observed in the ATR of glycerol.
Glycerol and O2 presented complete conversion in all condi-
tions analyzed, and in all cases were observed H2O
production.
Dry reforming
Fig. 12 presents the effects of the temperature (Fig. 12(a)),
pressure (Fig. 12(b)) and glycerol/CO2 molar composition in the
feed stream (Fig. 12(c)) over the DR of glycerol.
The effect of temperature was evaluated at constant
pressure (1 bar) and at constant glycerol/CO2 molar ratio (1.0/
1.0), and the results obtained are presented in Fig. 12(a). This
reforming technology presents a peculiar feature in relation to
other technologies evaluated; the CO molar ratio was high and
H2/CO relation is close to one for temperatures higher than
973.15 K. This behavior was expected due to high amounts of
carbon (as CO2) in the feed stream.
As observed in the other reforming technologies, the H2
and syngas production significantly increased with increases
in the operational temperature. Hydrogen production
Fig. 11 e H2/CO molar ratio for the autothermal reforming
of glycerol as function of glycerol/H2O/O2 molar ratio in the
feed. Simulation conditions: pressure: 1 bar; temperature:
973.15 K.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4 17979

reforming processes analyzed here. The effects of tempera-

ture and pressure on the solid carbon formation were pre-
sented at Fig. 13(a) and (b) respectively.
The elevation of the temperature results in the reduction of
the solid carbon formation; the simulations were performed at
constant pressure of 1 bar and constant glycerol/CO2 molar
ratio, of 1.0/1.0. The elevation of the operating pressure pre-
sents a negative effect, favoring the formation of solid carbon
in the system; the simulations were performed at constant
temperature (973.15 K) and constant glycerol/CO2 molar ratio
(1.0/1.0). These effects were also observed in the partial
oxidation of glycerol too.
The DR of glycerol presented the highest production of CO
among all reforming processes analyzed, this behavior can be
explained by the increase of the C and O atoms in the feed.
The formation of small amounts of C2H4 and C2H6 were
observed in conditions of elevated pressure (above 3 bar) and
low temperatures (below 873.15 K), in that conditions signifi-
cant amounts of solid carbon was also observed.

Supercritical water gasification

The proposed model was used to evaluate the SCWG reaction.
The effects of temperature, pressure and inlet glycerol
composition were analyzed and the results are presented
in Fig. 14(a)e(c), respectively.
The effect of modifications in the operating temperature
was analyzed at constant pressure of 250 bar and at constant
glycerol/water molar ratio (1.0/0.9, that is the same of 36.2 wt
%) and the results are presented at Fig. 14(a).
The elevation of the operating temperature resulted in
increased production of H2 in the system, as has been

Fig. 12 e Hydrogen, carbon monoxide and syngas molar

composition in the dry gas for dry reforming of glycerol as
function of (a) temperature; (b) pressure and (c) glycerol/CO2
molar ratio.

increases with increases in the temperature and reaches the

maximum at 1073.15 K.
The effect of operating pressure was studied at constant
temperature (973.15 K) and feed composition (1.0/1.0 e glyc-
erol/CO2). Higher pressures have a negative effect on
hydrogen and syngas production, the maximum amounts of
hydrogen and syngas were achieved at atmospheric pressure.
Fig. 12(c) presents the H2, CO and syngas composition in
dry gas as a function of glycerol/CO2 molar ratio in the inlet-
stream at constant temperature and pressure of 973.15 K and
1 bar, respectively. The addition of CO2 results in significant
increases of 61% in number of moles of CO produced in the
reaction. The addition of CO2 presents another interesting
effect, the reduction of solid carbon formation at constant
temperature.
The dry reforming of glycerol was the process that showed Fig. 13 e Solid carbon formation in the dry reforming of
greater susceptibility to solid carbon formation from all glycerol as function of temperature (a) and pressure (b).
17980 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

temperature (973.15 K) and constant glycerol/water molar

ratio (1.0/9.0).
The elevation of the operational pressure has no significant
effect on the production of H2 or syngas. Similar results were
observed in previous published papers of our group for the
SCWG of glucose, cellulose and microalgal biomass [62,71].
The effect of the feed concentration over the production of
H2 and syngas is presented in Fig. 14(c) as function of the mass
concentration of glycerol in the feed. The simulations were
performed at constant pressure and temperature of 250 bar
and 973.15 K respectively. The addition of glycerol results on
reduced productions of H2 and slightly increased the produc-
tion of CO.
This characteristic of the SCWG reaction is interesting
when the H2 production is the main objective, because the low
concentration of CO in the system facilitate the subsequent
separation processes [46].
The SCWG reaction had the lowest CO formation from all
processes evaluated. The excess of water used can explain
this behavior. The water reacts with the CO formed through
the water gas shift reaction (Eq. (4) in Table 1) to produce CO2
and more H2. In previous works of our group, the use of CO2 as
a co-reactant proved to be an effective way to improve the CO
production in the SCWG of different biomass materials [62,71].
Significant amounts of CH4 are observed at low tempera-
ture conditions (873.15 and 973.15 K). At 873.15 K, the main
products are CH4 and CO2, with the elevation of reaction
temperature H2 become the main product in the SCWG of
glycerol. The high pressures used in this process could explain
the formation of small amounts of C2H4, C2H6 and C3H8
especially at low temperatures. In any of the conditions
analyzed was observed the formation of solid carbon.
In the following section, all technologies were compared
with respect to hydrogen and syngas production.

Comparison between the technologies

Fig. 14 e Hydrogen, carbon monoxide and syngas molar
composition in the dry gas for supercritical water
gasification of glycerol as function of (a) temperature; (b)
pressure and (c) glycerol/water molar ratio.
observed in all other processes analyzed. The CO formation
also increased with increasing temperature, shuffled
remained low throughout the range of temperature analyzed.
Fig. 14(b) shows the effect of modifications in the operating
pressure on the composition of H2, CO and syngas in the
product stream, the simulations were performed at constant
Table 5 shows the better conditions for H2 production
observed in all reaction analyzed with the operational tem-
perature fixed at 1073.15 K. The SR, PO, ATR and DR were
analyzed at 1 bar and the SCWG was analyzed at 250 bar.
Analyzing Table 5 it’s interesting to emphasize that higher
molar fraction of H2 was observed in the SR reaction (with a
molar ratio glycerol/water ¼ 1.0/3.0 in the feed stream). The
lower molar fraction of H2 was observed for the SCWG reac-
tion. However this process presented the lowest production of
CO between all processes analyzed, with that, the subsequent
purification processes of H2 become simpler for the SCWG.

Table 5 e Better conditions for H2 production for the different reforming technologies analyzed.
Process Pressure (bar) Temperature (K) Molar ratio Molar fraction
H2 Syngas
SR 1 1073.15 1/3 (Gly/H2O) 61.9 88.4
PO 1 1073.15 1/0.5 (Gly/O2) 52.9 92.8
ATR 1 1073.15 1/1/1 (Gly/H2O/O2) 51.0 81.5
DR 1 1073.15 1/1 (Gly/CO2) 46.2 92.7
SCWG 250 1073.15 1/9 (Gly/H2O) 40.5 48.2
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4 17981

Table 6 e Better conditions for syngas production for the different reforming technologies analyzed.
Process Pressure (bar) Temperature (K) Molar ratio Molar fraction Ratio Moles
H2 Syngas H2/CO C(s)
SR 1 1273.15 1/3 (Gly/H2O) 60.8 91.4 1.99 0.00
PO 1 873.15 1/0.5 (Gly/O2) 46.5 65.4 2.44 0.65
ATR 1 973.15 1/1/1 (Gly/H2O/O2) 51.6 78.0 1.95 0.00
DR 1 873.15 1/1 (Gly/CO2) 41.7 62.5 2.00 1.16
SCWG 250 1273.15 1/9 (Gly./H2O) 57.7 75.7 3.21 0.00

The better conditions observed for syngas production (with
a molar ratio more close to 2.0 as possible) was presented
in Table 6. The SR, PO, ATR and DR were analyzed at 1 bar and
the SCWG was analyzed at 250 bar again. Each case presented
a different temperature of reaction to the better condition for
syngas production.
Analyzing Table 6 it is interesting to emphasize that the
highest molar fraction of H2 was observed to the SR reaction
(91.4% of the dry gas), with 1273.15 K of operational temper-
ature and with a glycerol/water molar ratio of 1.0/3.0, in that
conditions the H2/CO molar ratio was 1.99.
The SCWG of glycerol presented the highest H2/CO molar
ratio between all analyzed processes, 3.21 at 1273.15 K and
with a glycerol/H2O molar ratio of 1.0/9.0.
The lower molar fraction of syngas was observed for the
dry reforming of glycerol (62.5%) at 873.15 K and with a glyc-
erol/CO2 molar ratio of 1.0/1.0, in that conditions the H2/CO
molar ratio was 2.00, however was observed solid carbon
formation (1.16 mol of C(s)). Solid carbon formation was
observed in the PO too (0.65 mol of C(s) at 873.15 K and with a
glycerol/O2 molar ratio of 1.0/0.5).
Table 7 shows the comparison between all reforming pro-
cesses with respect to H2 and CO production and the results
obtained for the H2/CO molar ratio. The same glycerol/X
(where X are H2O, O2, CO2 or combinations between then)
molar ratio (1.0/3.0) was used in all simulations performed.
The SR, PO, ATR and DR were simulated at 1 bar and the
SCWG was simulated at 250 bar and three operational tem-
peratures (873.15, 973.15 and 1073.15 K) were evaluated.
Analyzing Table 7 it’s possible to verify that the highest
concentrations of H2 are observed in the steam reforming
reaction. Still in Table 7 it’s possible to verify that the SR and
ATR presented H2/CO molar ratio close to 2.0 in the conditions
in which the reactions were analyzed. The SCWG presented
the highest H2/CO molar ratio between all reforming pro-
cesses analyzed.
Another interesting effect is that the elevation of opera-
tional temperature results in reductions of the H2/CO molar
ratio in the product, by inducing the production of CO in the
system. This behavior was observed in all reforming processes
analyzed.
Conclusion
A thermodynamic analysis for hydrogen and syngas produc-
tion from glycerol using different reforming technologies has
been performed. The SR, PO, ATR, DR and SCWG were evalu-
ated. The composition of the products was calculated using
the Gibbs energy minimization approach in combination with
the virial equation of state.
The model was validated with simulated and experimental
data obtained in literature with good agreement between
then.
Hydrogen yields were found to increase directly with
temperature in all reforming processes analyzed. The increase
of the operating pressure results in large amounts of solid
carbon in the product stream in the partial oxidation and dry

Table 7 e Comparison between all reforming technologies of glycerol.

Reforming technology Temperature (K) Pressure (bar) Molar fraction (mol%) Molar ratio
H2 CO Syngas H2/CO
SCWG 873.15 250 8.5 1.6 10.1 5.34
973.15 250 15.8 4.7 20.6 3.34
1073.15 250 25.3 10.5 35.7 2.42
SR 873.15 1 55.0 14.8 69.8 3.72
973.15 1 61.7 23.0 84.8 2.68
1073.15 1 61.9 26.5 88.4 2.34
ATR 873.15 1 46.1 14.5 60.6 3.17
973.15 1 47.8 21.0 68.8 2.28
1073.15 1 46.3 25.3 71.5 1.84
OR 873.15 1 19.8 6.8 26.6 2.92
973.15 1 17.9 9.5 27.4 1.88
1073.15 1 16.0 12.0 28 1.34
DR 873.15 1 29.0 24.7 53.7 1.17
973.15 1 32.1 43.7 75.8 0.73
1073.15 1 31.8 47.7 79.4 0.67
17982 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 9 ( 2 0 1 4 ) 1 7 9 6 9 e1 7 9 8 4

reforming processes. In the other processes the formation of Subscripts

solid carbon was not observed. i refers to component i
The syngas production with H2/CO molar ratio close to 2.0 m refers to element m in a component
was found without solid carbon formation only in the steam
reforming of glycerol. Greek symbols
The proposed model implemented in the GAMS software m chemical potential
and solved with the CONOPT solver, show to be fast and m0i chemical potential of component i at reference
reliable (since computational time close to 1 s were observed condition
in the simulations and the validation with experimental and m0CðsÞ Chemical potential of solid carbon at reference
simulated data obtained in the literature showed that the condition
model presents a good predictive ability) to perform the fi fugacity coefficient of component i
thermodynamic analysis of the different glycerol reforming bi
f fugacity coefficient of component i in the mixture
technologies analyzed. u acentric factor

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