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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

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Thermodynamic study of the supercritical water reforming

of glycerol

F.J. Gutiérrez Ortiz*, P. Ollero, A. Serrera, A. Sanz

Departamento de Ingenierı́a Quı́mica y Ambiental, Universidad de Sevilla, Camino de los Descubrimientos, s/n, 41092 Sevilla, Spain

article info abstract

Article history: Hydrogen can be produced by steam reforming, partial oxidation, autothermal, or aqueous-
Received 15 March 2011 phase reforming processes using various noble metal based catalysts, but also by super-
Accepted 14 April 2011 critical water (SCW) reforming. Using AspenPlus
, a systematic thermodynamic analysis
Available online 18 May 2011 of glycerol reforming using supercritical water has been carried out by the total Gibbs free
energy minimization method, which computes the equilibrium composition of synthesis
Keywords: gas (syngas). The predictive SoaveeRedlicheKwong equation of state (EOS) has been used
Reforming as thermodynamic method in the simulation of the supercritical region, after evaluating it
Supercritical water against other EOS methods. A sensitivity analysis has been conducted on supercritical
Thermodynamic analysis water reforming of pure and pretreated crude glycerol, as obtained from biodiesel
Equation of state production. The effect of the main operating parameters (temperature, concentration of
Glycerol glycerol feed, glycerol purity in the feed of crude glycerol, and pressure) aimed to the
Biodiesel hydrogen production has been investigated in the reforming process, by obtaining the mole
fraction and molar flow-rate of components in syngas, as well as the hydrogen yield.
Selectivity to the different compounds has been also calculated. By this way, the ther-
modynamic favorable operating conditions at which glycerol may be converted into
hydrogen by SCW reforming have been identified. The simulation results agree well with
some few experimental data from the literature. This study is the first of a series addressed
to glycerol reforming using SCW.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction unreacted mono-, di-, and triglycerides, and methyl esters.

In recent years there have been intensive efforts toward the
development of novel technologies for the production of
hydrogen from renewable resources, mainly biomass. Among
the various biomass-derived compounds proposed as feed-
stock for hydrogen production, glycerol (C3H5(OH)3) is of
special interest because it is produced in large amounts (10 wt
%) as by-product of the chemical reaction (transesterification)
in which vegetable oil is processed into biodiesel. By-product
glycerol comprises a mixture of several other constituents,
such as methanol, water, inorganic salts, free fatty acids,
Conventional options for crude glycerol consist of refining it to
a higher purity. Unfortunately, the rapidly expanding market
for biodiesel cannot accommodate the excess amounts of
glycerol generated altering thus the cost and availability of
glycerol. However, glycerol production and utilization has
a great impact on both the economic stability and sustain-
ability of biodiesel production that will continue to increase as
the industry grows. As such, for utilizing the glycerol by-
product it is crucial to develop innovative processes.
The valorization of the crude glycerol, while avoiding the
application of expensive purification processes, will allow

* Corresponding author. Tel.: þ34 95 448 72 68; fax: þ34 95 446 17 75.
E-mail address: fjgo@esi.us.es (F.J. Gutiérrez Ortiz).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.04.095
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
augmented profitability of the biodiesel plants. One promising
and economical alternative is the transformation of glycerol
into an energy derivative as, for instance, to use it as
a renewable source of hydrogen, which is often defined as the
future energy carrier. This can be done with the use of several
methods including some reforming processes. Besides,
establishing a technology for hydrogen production from this
waste is desirable from the perspective of reduction of fossil
fuel consumption for power generation.
By now, glycerol reforming has been extensively studied
and an evaluation of these studies appears attractive. Three
types of glycerol reforming processes e steam reforming
[1,2], aqueous-phase reforming [3], and autothermal reform-
ing [4] e have primarily been investigated, but the glycerol
reforming by using supercritical water (SCW) has been barely
studied from a thermodynamic point of view, and even less
using not pure but crude glycerol.
Reforming reactions are generally endothermic, and
a reforming process may be characterized depending on the
source of heat and types of reactants. A general equation to
describe glycerol reforming is shown in reaction (1).
C3 H8 O3 þ xH2 O ¼ aCO2 þ bCO þ cH2 O þ dH2 þ eCH4 þ .
The equilibrium composition depends upon the reactant
ratios as well as the reaction temperature and pressure.
Reforming products include hydrogen and carbon monoxide
in addition to carbon dioxide and methane. A catalyst is nor-
mally used to accelerate the reactions in the reforming
process. Ni, Co, Ni/Cu, and noble metal (Pd, Pt, Rh) based
catalysts all favor hydrogen production, with Ni being the
most commonly used [5]. Catalysts boost the reforming reac-
tion rates at the molecular level and many thorough discus-
sions of the topic are available in the literature.
Glycerol steam reforming is the more popular reforming
process, and it can be represented by the overall reaction (2):
C3 H8 O3 þ 3H2 O ¼ 3CO2 þ 7H2
Thus, 7 mol of H2 are produced per mol of glycerol on the
reaction stoichiometry. Major concerns are by-product
formation (e.g., CO), catalyst deactivation, and high energy
consumption. There are more reforming processes and this
work is focused on reforming using supercritical water (SCW),
which is defined as water that is heated and compressed over
its critical temperature (374  C) and pressure (22.1 MPa).
Supercritical water (SCW) has properties very different
from those of liquid water. The dielectric constant of SCW is
much lower, the number of hydrogen bonds is much lower
and their strength is much weaker. As a result, SCW behaves
like many organic solvents so that organic compounds have
complete miscibility with SCW. Moreover, gases are also
soluble in SCW, thus an SCW reaction environment provides
an opportunity to conduct chemistry in a single fluid phase
that would otherwise occur in a multiphase system under
conventional conditions [6].
Gases like CO2, CH4, H2, and CO are completely miscible in
supercritical water [7,8]. The polar inorganic compounds like
KCl, NaCl, CaSO4 etc., which have high solubility in subcritical
water, shows very low solubility in supercritical water. Thus,
it is relatively easy to separate them from the product. This
8995
allows the product of SCWG to leave the system free from the
salt. More details are available in the literature [9].
Supercritical water is characterized by its high ion product,
which implies high [Hþ] or [OH] concentration in supercrit-
ical water. This allows SCW act like an acid or base catalyst in
the reactions. Many organic chemicals that do not react in
water without the presence of strong acid or base catalyst may
readily react under the hydrothermal condition of SCW.
Reactivity of water increases in the neighborhood of the
critical point with or without a catalyst. Thus, the reforming of
glycerol to synthesis gas or syngas (SG) using supercritical
water under a catalyst-free process arises as a very interesting
alternative and it will be studied in a future experimental work.
Due to the unique properties of SCW, thermodynamic
equilibrium and high chemical reaction rates are possible. In
fact, using SWC may be an excellent means for extraction of
energy from biomass, and allows high hydrogen concentra-
tion in the product gas with suppression of char and tar
formation [10]. At temperature higher than 600  C and pres-
sure higher than that of its critical point, water becomes
a strong oxidant. As a result, carbon is preferentially oxidized
into CO2 although low concentrations of CO are also formed.
(1) The hydrogen atoms of water and glycerol, as biomass, are set
free and form H2. The gas product (syngas) consists of H2, CO2,
CH4 and CO. Thus, for the design of the reactor and separators,
the knowledge of phase equilibria is very important.
2. Aims and scope
The objective of a reforming process of crude glycerol is to
produce hydrogen; however selectivity to hydrogen remains
challenging due to subsequent reactions in the gas. Thermo-
dynamic studies are very important because they provide
information on conditions that are advantageous for
hydrogen production. Thus, the aim of this study is to
(2) examine hydrogen production by SCW reforming of pure and
crude glycerol, which comprises impurities that cause catalyst
deactivation. Firstly, a discussion about the most suitable
thermodynamic method to be used for the simulation of the
supercritical state is carried out. Then, by predicting the
synthesis gas composition (hydrogen, carbon monoxide and
others) at equilibrium condition in the reforming reactor,
a sensitivity analysis is performed to know the effect of the
main operating parameters on hydrogen yield, so as to ach-
ieve optimal conditions for glycerol SCW reforming that
maximize hydrogen production.
3. Equations of state and simulation of the
supercritical state
When the operating temperature is beyond the critical point,
the simulation tool used in this work, AspenPlus
, considers
a gaseous behavior for the stream. Likewise, for lower
temperatures the properties taken by this software corre-
sponds to a liquid. Therefore, in the supercritical region, the
error of some thermodynamic properties, like enthalpy and
entropy, should be quoted depending on their reference to the
liquid or vapor state, as considered by AspenPlus
. By checking
8996 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
and comparing the results provided by different thermody-
namic methods, previously discriminated based on their
rightness of use in supercritical state, the most suitable one to
be chosen is that providing minima deviations in properties
from liquid and vapor state. Besides, this is also essential as
a prior step for achieving a conceptual design of the process to
be studied with confidence, by carrying out energy analysis and
using a heat exchangers network for recovering the process
heat [11].
The most computationally straightforward and thermody-
namically consistent method for calculating high pressure
phase behavior is to select an equation of state (EOS) to model
both the liquid and vapor or supercritical fluid phases, in
opposition to those thermodynamic methods based on activity
coefficients, which cannot be used for phase equilibrium with
supercritical fluids due to the different manner that they treat
each phase, and hence they cannot represent the changes that
occur in the critical region in continuous form. The thermo-
dynamic method finally chosen for fugacity calculation was the
predictive SoaveeRedlicheKwong (PSRK) equation of state
[12,13], which is an extension of the SRK equation of state, and
uses the generalized MathiaseCopeman a-function. This
model uses the HolderbaumeGemehling mixing rules, which
can predict the binary interactions at any pressure. Using
UNIFAC, the PSRK method is predictive for any interaction that
can be predicted by UNIFAC at low pressure. The main advan-
tage of using PSRK equation of state is that it is more accurate in
the prediction of the binary interaction parameters and it gives
more satisfactory results for mixtures of non-polar and polar
components, as the case of the crude/pure glycerol and water
mixture. This choice has been weighed against other thermo-
dynamic methods such as the original SoaveeRedlicheKwong
(SRK), Peng-Robinson (PR) and Peng-Robinson with the Boston-
Mathias afunction (PR-BM).
The PSRK method represents quite accurately the super-
critical state for the glycerol and the CO2 (taking as a reference
since it is probably the fluid more studied in supercritical
Fig. 1 e Simulation of the supercritical state for glycerol and CO2 at 240 atm (PSRK method).
state), as shown in Fig. 1, although 240 atm is a pressure much
higher than critical pressure of glycerol (74.02 atm) and CO2
(72.86 atm). PR and PR-BM also give a very good fit and the SRK
shows small deviations, although these are not shown.
On the other hand, for the water, the PSRK method shows
the minimum deviation between the liquid and vapor curves
in the supercritical state (Fig. 2) of all the thermodynamic
methods tested. The absolute error for specific enthalpy
(difference between liquid and vapor curves) has been quoted
between 3 and 6 kJ/mol in the critical region, showing the
maximum deviation around 565  C. Although 6 kJ/mol may
not be considered as a large difference, it should be noted that
the glycerol should be very dilute in the reforming with SCW,
as after explained, so an error of 6 kJ/mol could become
a significant divergence from the energy standpoint. The PR
and PR-BM methods showed behaviors similar to that depic-
ted in Fig. 2 for PRSK, but the deviations are slightly higher.
Then, these methods could be also used with relative confi-
dence. However, the SRK method showed large errors.
For the glycerol, it has been verified that in the supercritical
state, the vaporization heat is saved, which is a very significant
energy saving and agrees well with data from literature [14,15].
This is illustrated in Fig. 3, where a specific energy saving of
47.3 kJ/mol is obtained when operating at 600  C and 240 atm,
which is lower than the glycerol vaporization heat (58.2 kJ/mol)
at its boiling point (1 atm, 290  C). However, the energy saving
continuously decreases as the temperature rises.
In the case of water, depicted in Fig. 4, there is an uncer-
tainty relative to the error due to the mismatch between the
enthalpies referred to vapor and liquid states for temperatures
higher than the critical temperature. This inconvenient may
be overcome by an average curve between the vapor and
liquid curves, with a maximum error of 3 kJ/mol, or by
directly taking the vapor curve as the valid one, since this
option corresponds to the minimum energy saving. The
increase in enthalpy is huge when changing from liquid to
vapor at atmospheric pressure. However, for the liquid at
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Fig. 2 e Evolution of the water trend in liquid and vapor state at 240 atm (PSRK method) - each enthalpy interval is 2 kJ/mol.

240 atm, it can be seen that when temperature rises to the
critical value, the slope of the curve rapidly increases. Beyond
this zone, the specific energy saving becomes 10.7 kJ/mol at
400  C (Fig. 4). Although this value is quite lower than that for
glycerol, there will be a significant energy saving due to the
heat up of the large amount of water required for the SCW
reforming of glycerol to maximize hydrogen yield, as below
exposed. However, by increasing the temperature from 400 to
800  C, the specific energy saving would decrease from 10.7 to
4.5 kJ/mol. Therefore, the energy saving is lower for temper-
atures much higher than 374  C. Besides, the energy analysis
should account for the mechanical energy necessary to raise
the pressure from atmospheric to supercritical values.
Fig. 5 illustrates the effect of pressure on simulation of the
supercritical state for the water, it can be seen that when the
pressure increases over the critical value, the vapor curve
exhibits a decrease in enthalpy at temperatures slightly under
the critical one in such a way that the liquid and vapor
enthalpies matches just in the critical point. Besides, when the
pressure is twoethree times higher than critical pressure, the
vapor and liquid states match well for supercritical tempera-
tures. In Fig. 6 a more narrow range of temperatures has been
used in order to get better accuracy in the cited vapor behavior
around the critical point under different pressures. Thus, it
was carried out an analysis between 350 and 400  C using
temperature increments of 0.10  C (500 point data versus the

Fig. 3 e Vaporization heat (l) and energy saving for the glycerol at 240 atm. The blue curve represents the vapor state at
atmospheric pressure and it is taken as a reference in the computation of the energy saving. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
8998 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

Fig. 4 e Vaporization heat (l) and energy saving for the water (supercritical pressure of 240 atm).

previous figures that is 100 point data). These analyses were
done for both subcritical and supercritical conditions. At 210
and 215 atm, the enthalpy curves for liquid and vapor phases
are not still concurrent. At 218 atm, the curves match each
other just at 374  C. At pressures higher than the critical one,
the enthalpy curve tends to abruptly diminish just at 374  C,
where it matches with the liquid curve. Next, a unique curve is
shown. The sudden enthalpy drop of the vapor curve at the
critical temperature for pressures higher than the critical is
quite sound. The reason is because the thermodynamic
method used is based on an EOS where, by definition, the
fugacity of liquid and vapor in the critical point must be equal.
This implies that all the properties must be equal in this point,
and so the enthalpy. By this way, it has been obtained
a decrease in enthalpy as the temperature increases inside
a given range just before reaching the critical point, which is
not thermodynamically reasonable. The explanation of this
simulated behavior is due to the vapor curve for water is not
real at temperatures lower than the critical under pressures
higher than the critical. That is, at pressures as high as those

Fig. 5 e Enthalpy variation for water in liquid and vapor phase at 220, 300, 600 and 800 atm.
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
Fig. 6 e Enthalpy variation between 350 and 400  C for water in liquid and vapor phase at 210 and 215 atm (subcritical
conditions), 218 atm (critical conditions), and 220, 240, 400 and 600 atm (supercritical conditions).
used in these analyses, the water must be in liquid phase. As
a consequence, although AspenPlus
provides results for the
vapor curve in any interval of temperatures, the part of the
vapor curve to be rightly used is that just over the critical point,
i.e., the part relative to the supercritical region. Likewise, the
rapid increase of the liquid enthalpy around the critical
temperature found for pressures around the critical pressure
becomes negligible at pressures higher than 400 atm, where
supercritical state is more clearly distinguished from the
subcritical state.
Finally, a sensitivity analysis for the case of water was
carried out to study the transition from the subcritical to
supercritical state starting at a given pressure. Results are
shown in Fig. 7, in an HeP diagram, where it can be seen that
there is a decrease in the enthalpy corresponding to the
vaporization heat due to phase change from vapor to liquid for
all the isothermal curves, except at 400 and 500  C (values
higher than the critical temperature). This vaporization heat
decreases when temperature approaches to the critical one
(374  C), where becomes null. Beyond the critical point,
enthalpy slightly decreases as pressure rises.
4. Methodology of the thermodynamic
analysis
For given operating conditions, the equilibrium compositions
in the reforming reactor have been calculated. The
8999
computation has been made with the aid of AspenPlus

version 2006.5 [16]. In this study, an R-Gibbs reactor has been
used to calculate the products composition and the heat of
overall reaction in a system under the conditions that mini-
mize of Gibbs free energy. This is a non stoichiometric
approach, where a selection of the possible set of reactions is
not necessary and does not require any initial estimation of
the equilibrium. Indeed, the method of minimizing the Gibbs
free energy is normally preferred in fuel-reforming analysis,
especially when the reaction temperature and pressure are
specified. The R-Gibbs reactor does not take reaction kinetics
into account and allows individual reactions to be at
a restricted equilibrium.
The thermodynamic analysis ignores and does not provide
kinetics effects of reactions taking place, and it assumes
equilibrium. Although a practical situation may diverge, the
results of the analysis provide a valuable reference on optimal
conditions for hydrogen production so as to design experi-
mental tests and compare the results from these.
4.1. Process simulated
The simulated process is illustrated in Fig. 8. The flow-sheet
consists of a high pressure pump for the glycerol-water
mixture, obtained in a mixer and a heater in order to respec-
tively get the pressure and temperature specified for the
reforming reactor. It is assumed that reactor also operates by
providing the energy needed to hold the endothermic
9000 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
Fig. 7 e Enthalpy of water as function of pressure at constant temperature (100, 200, 300, 350, 400 and 500  C).
reactions so as to operate at the specified temperature.
Hydrogen, carbon monoxide, carbon dioxide, methane,
ethane, propane, water, methanol, ethanol and glycerol as
well as pure carbon were manually added for being considered
as the possible species in SCW reforming of glycerol. The
simulation did not predict coke formation for any of the
experimental conditions in this paper, and it did not add any
other compound (mole fractions lower than 1020). Next, an
expander (turbine) is included to reduce the pressure in an
efficient way. Downstream from the expander, a cooler
diminishes the temperature to 200  C. Then, an Equilibrium
reactor (Requil) is used to model the wateregas shift reaction to
increase the conversion to hydrogen in the syngas and to
reduce the CO content, which poisons the anode of proton
exchange membrane fuel cells (PEMFC). Requil operates with-
drawing the energy released from the exothermic reaction so
as to operate at the specified temperature. The outlet stream is
after cooled to 60  C in another cooler to drive, e.g., the gas to
a PEMFC where hydrogen would be converted into electrical
energy. Finally, a flash separator is included to separate liquid
W
HEAT1
R1
B1 PUMP
02 03
01
04
B2
GLY
05
Fig. 8 e Flow-sheet of the simulated process.
condensates from the gaseous phase. Pressure reduction
should not be made after cooling to 200  C because another
separator should be added, prior to expansion, where there
would be a significant fraction of hydrogen removed in the
liquid outlet stream and, hence, an important yield lost.
Specifications of elements used in the simulation are shown
in Table 1. As aforementioned, the thermodynamic method
used has been the predictive SoaveeRedlicheKwonge(PSRK).
This method was contrasted against UNIFAC and Ideal
methods for the low pressure zone of flow-sheet downstream
from the expander (operating at about atmospheric pressure),
but results are undisturbed, so for the sake of simplicity, PSRK
method was used for all the simulation.
4.2. Crude glycerol simulated
Two feeds have been considered: pure and pretreated crude
glycerol. Normally, 1:6e1:9 M ratios of oil-to-methanol are
used in the transesterification of vegetable oil to biodiesel with
catalyst NaOH. After the reaction is finished, large amount of
SEP SG4
C OOL2
R2 SG2 SG3
C OOL1
SG1
W2
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concentration for both the pure and the pretreated crude

Table 1 e Specifications of the components for the
simulation. glycerol. In addition, for this latter, a sensitivity analysis has
been performed for the MeOH content in the crude glycerol,
Code Equipment Specifications
as a measure of the glycerol purity of crude feed. The total
B1 Mixer molar flow-rate fed to the system is always 1000 mol/h. The
PUMP Pump Outlet pressure: Variable analyses were carried out over the following variable ranges:
HEAT1 Heat exchanger Pressure drop: 0.2 atm.
temperature of 400e1000  C, glycerol to feed (glycerol plus
Outlet temperature ¼ Variable
water) mole ratio of 1e16 (990 mol/h water and 10 mol/h
R1 Reactor Inlet temperature: Variable
Outlet temperature ¼ Inlet glycerol e 840 mol/h water and 160 mol/h glycerol) and
temperature pressure ranging from 200 to 300 atm, for both pure and
Pressure drop: 0.22 Pa pretreated crude glycerol. MeOH content in the crude glycerol
B2 Expander Isentropic turbine was changed from 10 to 30 wt%. Selectivity results are
Outlet Pressure: 1.4 atm. analyzed for the reactor outlet stream (4) and the hydrogen
COOL1 Heat exchanger Outlet temperature: 200  C
yield is referred to this stream as well as to the outlet stream
Pressure drop: 0.2 atm.
of the WGS reactor (stream SG2), so as to include the global
R2 Reactor Inlet temperature: 200  C
Outlet temperature ¼ Inlet process.
temperature In the simulation results, the contents of ethane,
Reaction: H2O þ CO ¼ H2 þ CO2 propane and ethanol have been grouped as the content in
COOL2 Heat exchanger Outlet temperature: 60  C organic carbon different of methane (namely Others), due to
Pressure drop: 0.2 atm. in all the cases the concentration of those compounds at
SEP GaseLiquid Outlet temperature ¼ Inlet
the reactor outlet are quite lower than those corresponding
separator temperature ¼ 60  C
to the other compounds. In addition, at glycerol to feed
mole ratios used from 1 to 16, carbon formation is predicted
the methanol is unreacted. Since methanol and glycerol both to be thermodynamically inhibited at any temperature
have carbon-to-alcohol ratios of 1:1 with associated high analyzed in this study, due to the high proportion of water,
degrees of hydrogen bonding, the methanol preferentially and so the carbon (graphite) production is insignificant and
distributes into glycerol phase, and only a relatively small not shown.
amount dissolves in biodiesel, as experimentally verified [17].
Indeed, the main components of crude glycerol are glycerol 5.1. Effect of the reaction temperature
and methanol [18], and also water [19], which is used to reduce
its viscosity and allow the crude glycerol to be pumped. Reaction temperature is perhaps the most important param-
Anyway, in order to better perform the reforming process, an eter that influences the performance of SCW reforming of
economic solution for the partial purification of crude glycerol glycerol. It is expected to have a significant effect on the
stream should be done, especially to reduce the negative process yield, especially in absence of catalyst [15]. To avoid
impact on catalyst and reactor material under supercritical the use of a catalyst, which becomes essential for low
conditions. Thus, in this study it is assumed that de crude temperature processes, the present study only considers high
glycerol is pretreated to remove high salt (it may be very temperatures. So, the uncatalyzed reforming will need high
corrosive) and free fatty acid content as well as methyl esters temperature (500e800  C, and even more), although it is less
impurities (these two latter may be converted into undesired efficient than that at low temperature from the energy and
tar and coke [10]), e.g., by neutralization. The salt formed exergy point of view, since external energy may be needed to
during this phase may be recovered for use as fertilizer, after sustain the process.
precipitation and filtration. Furthermore, the methanol may The overall reforming yield depends on chemical reactions
be stripped from this stream to be recovered and reused. Thus, involved and their rate. The product gas composition would be
this pre-treatment would produce a stream with >80 wt% governed by the chemical equilibrium of the reactions
pure glycerol. Therefore, a pretreated crude glycerol consists involved. Since the reaction rate constant would increase with
of glycerol (80 wt%), methanol (20 wt%) and no water has been temperature, the overall reforming yield would be higher and
considered in this study. The possible water content in the its rate of increase with time would also increase as temper-
pretreated crude glycerol feed is included inside the water ature does so. On the other hand, the reaction of complete
stream, and thus an anhydrous crude glycerol feed is referred conversion of glycerol to hydrogen is endothermic while the
in this work. reaction that completely converts glycerol to methane is
The upper concentration of MeOH has been limited to 30 wt slightly exothermic. Thus, on equilibrium conditions and
% in the crude glycerol, as a realistic value, since the MeOH according to the Le Chatelier principle, the methane forma-
recovery is essential for the economy of a biodiesel production tion increases at lower temperature. CH4 competes against H2,
plant. and obviously, CH4 is not a desirable product if the ultimate
goal is hydrogen production. As a consequence, it is clear that
high reforming temperatures are recommended.
5. Results and discussion Since the minimum operating temperature is the critical
(374  C), the effect of the temperature has been analyzed on
A sensitivity analysis has been carried by varying operating the equilibrium of the different reactions taking place in the
pressure and temperature as well as the glycerol feed reactor by varying in increments of 50  C, between 400 and
9002 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
1000  C. The pressure was kept at 240 atm and the glycerol
concentration in the feed was always 1 mol % (5 wt%).
Results are shown in Figs. 9 and10 relative to streams 4 and
SG2 (outlet of the reformer and WGS reactor respectively) for
both pure and pretreated crude glycerol. These figures
represent the equilibrium mole fraction of the gaseous
products in dry basis as a function of temperature. For the
pure glycerol, it is depicted that the mole fraction of
hydrogen increases with the increase in the temperature up
to a maximum value and then it is approximately constant
(about 0.689) in R1, and 0.696 at the outlet of R2, very next to
maximum value according to the stoichiometry of the reac-
tion (3), as CH4 and CO are insignificant, due to the operating
conditions that does not promote the methane production
and to the huge excess of water, which consumes near all of
carbon monoxide. In addition, the reaction (3) is endo-
thermic, so it is very shifted to the right side at high
temperatures.
overall glycerol reforming:
C3 H5 ðOHÞ3 þ3H2 O ¼ 3CO2 þ 7H2
glycerol decomposition:
C3 H5 ðOHÞ3 ¼ 3CO þ 4H2
wateregas shift:
CO þ H2 O ¼ CO2 þ H2
As expressed by reactions (3a) and (3b), overall glycerol
reforming may be represented as a first stage of glycerol
decomposition followed by a wateregas shift reaction.
In Figs. 9 and 10, it can be also observed that the mole
fraction of CH4 decreases with the increase in the tempera-
ture, mainly because the high temperatures favors its thermal
decomposition forming hydrogen and CO2 in the presence of
water, as it can be seen in the reaction (4).
methane steam reforming:
CH4 þ H2 O ¼ 3H2 þ CO
Likewise, the mole fraction of CO2 decreases with the
increase in the temperature because at high temperature the
reaction between CO2 and CH4 is promoted thus producing CO
and H2, on the reaction (5).
methane dry reforming:
CO2 þ CH4 ¼ 2H2 þ 2CO
At higher temperatures, this endothermic reaction is favored
and therefore CO2 produced is after consumed. Indeed, reac-
tions (3)e(5) are endothermic so an increase in temperature
will provide a shift of the equilibrium toward the products
(right side of reactions). Table 2 shows the reaction enthalpy
for these three reactions (3)e(5), obtained for both standard
conditions (298 K and 1 atm) and nominal operating condi-
tions (800  C and 240 atm).
The rest of organic compounds (grouped in Others) present
a concentration much lower than 0.01 mol %, so these
compounds can be considered as insignificant and be
neglected. As a result, the more likely expected products are
CO, CO2, CH4 and H2. In addition, CO will practically disappear
in the wateregas shift (WGS) reactor (R2).
The reactions of methanol reforming (6) and decomposi-
tion (7) are the following:
methanol reforming:
CH3 OH þ H2 O ¼ CO2 þ 3H2 (6)
methanol decomposition:
CH3 OH ¼ CO þ 2H2 (7)
For pretreated crude glycerol reforming the results are very
similar to those obtained for pure glycerol, especially relative
to the mole fraction of hydrogen, although the mole flow-rates
are lower according to reactions (3) and (6).
On reactions (3) and (6), hydrogen yield are computed for
pure and pretreated crude glycerol as follows (Eq. (8) and (9)):
mol=h H2 1
hpure ¼  (8)
mol=h C3 H5 ðOHÞ3 7
mol=h H2
hcrude ¼ (9)
mol=h C3 H5 ðOHÞ3 7 þ mol=h CH3 ðOHÞ  3
(3)
Thus, Figs. 9 and 10 also illustrate the hydrogen yield in the
reforming reactor (R1) and for the overall process. The glycerol
and methanol conversion were always 100%, at equilibrium
(3a)
condition. Between 750 and 800  C, the hydrogen yield becomes
approximately constant and equal to 95%, at the R1 outlet,
achieving 99% in the WGS reactor at 200  C and 1 atm. Likewise,
(3b) a maximum value is reached for 900  C in R1 (95.9%), and the
hydrogen content scarcely changes for temperatures greater
than 900  C. Anyway, for a practical purpose, beyond 800  C the
yield can be considered as constant, and thus a temperature
higher than 800  C would be unnecessary. For the pretreated
crude glycerol, the hydrogen yield should be referred to the sum
of glycerol and methanol, so as to avoid to get efficiencies
higher than 100%. With respect to the pure glycerol, for pre-
treated crude glycerol relatively higher hydrogen yields are
obtained although hydrogen production (molar flow-rate) is
lower, due to the methanol presence, which reforms better but
(4) produces less hydrogen than glycerol.
A case study was performed (but not shown) by consid-
ering a feed with a 16 mol % of pretreated crude glycerol with
a 10 wt% methanol, and very low mole fraction of hydrogen as
well as very high increase in methane production were ob-
tained. Moreover, it was verified that at temperatures lower
than 750  C, hydrogen yield is lower than 20%, and almost the
(5) main production is methane and carbon dioxide.
5.2. Effect of glycerol concentration in the feed
An interval from 1 to 16 mol % (about 5e50 wt%) of glycerol
concentration in the feed, with water being the rest, has been
studied at 240 atm and 800  C. For the pretreated crude glycerol,
20 wt% is methanol. Results are represented in Fig. 11 and 12,
which depict gas concentration at the outlet of the reforming
reactor (R1) and the WGS reactor (R2) as a function of glycerol
feed concentration for pure and pretreated crude glycerol. It
can be observed that the mole fraction and the molar flow-rate
of methane increase as well as the mole fraction of hydrogen
decreases and its molar flow-rate increases as the glycerol feed
concentration rises. This is an expected result since a higher
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3 9003

Fig. 9 e Mole fraction (a), molar flow-rate (b) of the outlet gases and hydrogen yield (c) for a pure glycerol concentration in the
feed of 1 mol % at 240 atm. Streams 4 and SG2.
9004 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

Fig. 10 e Mole fraction (a), molar flow-rate (b) of the outlet gases and hydrogen yield (c) for a crude glycerol (20 wt% MeOH,
80 wt% C3H8O3) concentration in the feed of 1 mol % crude glycerol at 240 atm. Streams 4 and SG2.
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
glycerol concentration lessens the shift toward the right side of
reaction (3) due to the lower water surplus. Accordingly, the
reforming reaction to produce hydrogen compete against the
methanation reactions, in such a way that the produced
hydrogen is partially consumed by reacting with CO and CO2 to
produce CH4, as shown in reactions (10) and (11):
methanation of CO:
CO þ 3H2 ¼ CH4 þ H2 O
methanation of CO2:
CO2 þ 4H2 ¼ CH4 þ 2H2 O
The temperature also affects these two equilibria, moving
them to the left side when the temperature increases, because
of reactions (10) and (11) are exothermic. Thus, CH4 produc-
tion is inhibited by operating at high temperatures, as
aforementioned.
Mole fractions of CO and CO2 increase as glycerol concen-
tration increases in the feed, although not as much as CH4.
Anyway, CO2 mole fraction is quite higher than that of CO due
the wateregas shift reaction, which promotes the reaction (3b)
leading thus to CO2 production. Results for pretreated crude
glycerol are qualitatively similar to those obtained for pure
glycerol, and values of mole fraction for the product gases are
practically the same. The difference is found in the molar flow-
rate that is lower for a crude glycerol with higher content in
MeOH, since the number of carbon, hydrogen and oxygen atoms
is lower in the methanol for a given total feed molar flow-rate.
Moreover, Figs. 11 and 12 also illustrate that higher meth-
anol content in the crude glycerol relatively enhances the
hydrogen yield defined by Eq. (9), although hydrogen produc-
tion (molar flow-rate) is lower. If instead of using Eq. (8) and
(9), the hydrogen yield is expressed by the produced H2
molar flow-rate to (pure or crude) glycerol feed molar flow-
rate ratio, the values obtained for pure glycerol would be
higher than those for pretreated crude glycerol. Thus, with
regarding to R1 reactor, and in case of feeding pure glycerol,
6.66 mol of H2 are produced per mol of glycerol for a glycerol
concentration of 1 mol % (5 wt%), while at 16 mol % (49 wt%)
glycerol, the number of H2 moles produced per mol of glycerol
decreases to 1.44. For the crude glycerol with 20 wt% meth-
anol, the ratios are 5.17 and 1.39 mol of H2 are produced per
mol of pretreated crude glycerol, respectively. When the yields
are referred to R2 reactor, the ratios are 6.86 and 1.99 for pure
glycerol; 5.90 and 1.66 for crude glycerol, respectively.
Therefore, the process moves far from the optimum for
hydrogen production as the glycerol feed concentration
increases, but for low glycerol feed concentration the
unreacted water (as steam) dilutes hydrogen product. These
Table 2 e Reaction enthalpies for the main reactions taking place inside the reforming reactor under standard (298.15 K,
1 atm) and operating (1073.15 K, 240 atm) conditions.
Reaction Enthalpy standard cond. (kJ/mol)
(25  C, 1 atm)
C3 H8 O3 þ 3H2 O43CO2 þ 7H2
CH4 þ 2H2 O44H2 þ CO2
CO2 þ CH4 42H2 þ 2CO
9005
issues should be further inspected for an energy analysis of
the process, as it will be done in the next work.
Because of the high CO2 content in the syngas produced,
the dry reforming of methane (reaction (5)) will also proceed.
Dependent upon the water to methane ratio and CO2 content
in the syngas, CH4 is more or less reformed with H2O or CO2.
Thereby, the equilibrium of the wateregas shift reaction and
H2 and CO mole fraction in the synthesis gas are affected.
(10)
5.3. Effect of the methanol concentration in the crude
glycerol
(11)
Fig. 13 shows how the increase in MeOH concentration
(decrease in C3H5(OH)3 purity) of the crude glycerol leads to
a reduction of the molar flow-rate of hydrogen and carbon
dioxide for streams 4 and SG2. This effect is stronger if the
crude glycerol feed concentration was higher, in such a way
that hydrogen produced from the reforming of methanol is
less than that obtained from glycerol reforming, on reactions
(3) and (6). Fractions of MeOH in the crude glycerol should be
controlled at low values, not because of inefficient methanol
reforming, but to save it thus recovering and returning to the
biodiesel production process.
An increase of methanol fraction in crude glycerol makes
the concentration of CO and CO2 decrease very slightly as well
as does with the molar flow-rates of those compounds. There-
fore, the concentrations of carbon monoxide and carbon
dioxide are not practically affected by the variation of MeOH in
the feed concentration. The simulation results showed good
agreement with the theoretical results obtained by previous
studies regarding with the SCW reforming of methanol [20,21].
Moreover, in order to contrast the effect of methanol by mini-
mizing the effect of the high water dilution, another simulation
was also performed (but not illustrated in a figure) using 16 mol
% pretreated crude glycerol with variable MeOH content at
800  C and 240 atm. Apart from the low mole fraction and yields
of hydrogen as well as high production of methane, as expected,
the effect of MeOH as such was disclosed as insignificant (flat
curves) for the range tested (10e30 wt% MeOH).
5.4. Effect of the reaction pressure
According to some authors, the effect of pressure is negligible
in the supercritical region [14,21,22]. However, when the
pressure is below the critical pressure, the special physical and
chemical properties of water disappear. Likewise, higher
pressure causes trouble for the design and maintenance of the
system and also increases the operating and investment costs.
For it, a pressure range from 200 to 300 atm has been considered
by taking increments of 20 atm. By this way, the process is
Enthalpy operating cond. (kJ/mol)
(800  C, 240 atm)
358.01 192.42
252.85 197.64
247.00 260.87
9006 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

compared under subcritical conditions and the possible
advantages of increasing the operating pressure are evaluated,
from the thermodynamic point of view. The temperature was
kept in 800  C and the glycerol concentration in the feed has
been of 1 mol%. The simulation for crude glycerol is almost
equal to that of pure glycerol, and it has not been included in
this paper. Fig. 14 depicts the results of the simulation, for the
pure glycerol. In general, it can be observed that the pressure
barely affects the gas composition at the reformer outlet, even
for subcritical region. H2, CO2, CO and CH4 change all of them

Fig. 11 e Mole fraction (a), molar flow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the glycerol
concentration in the feed (pure glycerol) at 800  C and 240 atm. Streams 4 and SG2.
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3 9007

very slightly. Consequently, hydrogen yield and glycerol a margin over the critical pressure (218 atm) thus accounting
conversion are almost constant for the overall range of pres- for pressure drops in the equipment and through the pipes.
sures tested. Thus, 240 atm can be considered as a suitable However, values slightly lower than 240 atm should be exper-
pressure, taking into account that it is convenient to have imentally inspected.

Fig. 12 e Mole fraction (a) and molar flow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the glycerol
concentration in the feed (crude glycerol, 20 wt% MeOH and 80 wt% C3H8O3) at 800  C and 240 atm. Streams 4 and SG2.
9008 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

5.5. Selectivity computation (H2, CO, CO2 and CH4) were computed, for both pure and
pretreated crude glycerol, just at the reforming reactor outlet
Finally, in order to assess the reactions taking place inside (stream 4). For the pure glycerol, the selectivity computation
the reforming reactor (R1), selectivity to main compounds to component x was made by using Eq. (12), where the

Fig. 13 e Mole fraction (a) and molar flow-rate (b) of the outlet gases and hydrogen yield (c) as a function of the methanol
concentration (wt%) in the feed (crude glycerol, 1 mol %) at 800  C and 240 atm. Streams 4 and SG2.
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3 9009

Fig. 14 e Mole fraction of the outlet gases for a glycerol concentration in the feed (pure glycerol) of1 mol% glycerol at 240 atm
and an operating temperature of 800  C. Stream 4.

 
calculation for H2 and CO2 are shown as examples (Eq. (13)). nH2 xC3 H8 O3 xCH3 OH
SH2 ¼  þ  100 (14)
This equation was modified for hydrogen by referring it to nCO þ nCO2 þ nCH4 7=3 3=1
CO2 in reaction (3) that produces 7 mol of H2 per each 3 mol of
where xC3H8O3 and xCH3OHare the mole fraction of glycerol and
CO2.
methanol in the feed, respectively. Thus, it is weighted the
 mole ratio between H2 and CO2 in the reforming of glycerol (7/
no: C atoms in x
Sx ¼ (12) 3) and methanol (3/1), on reactions (3) and (6).
no: total C atoms stream 4
First, the selectivity analysis was performed for a nominal
nCO2
SCO2 ¼  100 and SH2 glycerol feed concentration of 1 mol% at 240 atm, and
nCO þ nCO2 þ nCH4
temperature was changed from 400 to 1000  C. Then, the
nH2 1
¼   100 (13) glycerol concentration was changed from 1 to 16 mol %, at
nCO þ nCO2 þ nCH4 7=3
800  C and 240 atm.
For a crude glycerol, a revised equation of selectivity to In Fig. 15, it can be observed as, for a pure glycerol feed,
hydrogen was derived from reactions (3) and (6) and then hydrogen selectivity increases with the increase in the reac-
used, as follows (Eq. (14)): tion temperature, and the methane selectivity decreases.

Fig. 15 e Selectivity of H2, CO, CO2 and CH4 as a function of the temperature for a glycerol concentration in the feed (pure
glycerol) of 1 mol% glycerol at 240 atm and an operating pressure of 240 atm.
9010 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3

Fig. 16 e Selectivity of H2, CO, CO2 and CH4 as a function of the temperature for a glycerol concentration in the feed (crude
glycerol, 20 wt% MeOH and 80 wt% C3H8O3) of 1 mol % crude glycerol at 240 atm.

Beyond 800  C, CH4 production is insignificant. For a temper-
ature higher than 750  C, CO2 selectivity begins to decrease,
probably due to the reformation of CH4 with CO2 following the
reaction (5). Similar trends are observed for pretreated crude
glycerol (Fig. 16), and main differences between this latter and
pure glycerol are in selectivity to hydrogen, about 850e900  C:
93.1 and 95.9%, respectively.
Fig. 17 and 18 illustrate the decrease in selectivity to
hydrogen as well as the rapid increase of selectivity to
methane when the glycerol feed concentration is increased.
Beyond the glycerol concentration of 8 mol %, CH4 selectivity
becomes higher than H2 selectivity, for pure glycerol. So, if the
product desired is hydrogen the glycerol feed concentration
should be reduced as much as possible. Likewise, CO2
selectivity decreases as glycerol feed concentration rises
while CO selectivity increases to reach a maximum at about
2e3 mol % pure glycerol and then decreases to 20%, remain-
ing constant in this value from about 6 to 16 mol %, due to the
reforming reaction is inhibited and promoted the methana-
tion reactions (8) and (9). For pretreated crude glycerol,
selectivity to CO rises to maximum (12.3%) at 2.8 mol % pure
glycerol, remaining constant for higher concentration of
glycerol.
Finally, selectivity evolution versus pressure was also
studied but it was verified a lack of dependence between both
variables, and so the simulation results are not shown.
Fig. 19 depicts a very weak effect of the methanol concen-
tration in the crude glycerol for all the compounds. Although

Fig. 17 e Selectivity of H2, CO, CO2 and CH4 as a function of the glycerol concentration in the feed (pure glycerol) at 800  C and
240 atm.
 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3 9011

Fig. 18 e Selectivity of H2, CO, CO2 and CH4 as a function of the glycerol concentration in the feed (crude glycerol, 20 wt%
MeOH and 80 wt% C3H8O3) at 800  C and 240 atm.

this figure shows the simulation results obtained by using
1 mol % crude glycerol, this is not due to the high proportion
of water because another simulation for 16 mol % glycerol
feed concentration was performed (but not shown) where
the concentration of MeOH was changed from 10 to 30 wt%
and no noticeable effect due to MeOH concentration was
observed.
5.6. Optimal conditions for maximum hydrogen
production
The maximum hydrogen yield is achieved at 900  C and for
a glycerol feed concentration of 1 mol %, combining thus low
carbon monoxide and methane yields. Carbon monoxide and
methane are considered undesirable products. CO affects the
overall size of the reforming process, especially the water-
egas shift reactors, and CH4 contains hydrogen, decreasing
thus the overall hydrogen production. The higher the mole
ratio of water to glycerol, the higher mole fraction of
hydrogen (in dry basis) is. The carbon monoxide is nearly
converted in the WGS reactor. However, the energy
consumption and the size of the units increase as water flow-
rate increases.
All the thermodynamic analyses agree well with the few
experimental results found in the literature [22], where at
dilute feed concentration (5 wt% glycerol), 6.5 mol of hydrogen/

Fig. 19 e Selectivity of H2, CO, CO2 and CH4 as a function of the methanol concentration (wt%) in the feed (crude glycerol,
1 mol %) at 800  C and 240 atm.
9012 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 6 ( 2 0 1 1 ) 8 9 9 4 e9 0 1 3
mol of glycerol was obtained at a temperature of 800  C and
pressure of 241 bar, over Ru/Al2O3 catalysts in a tubular fixed-
bed flow reactor. Therefore, if the real yields come close to
those calculated assuming equilibrium is because of a right
approach to equilibrium in real reactors is achieved.
6. Conclusions
Thermodynamic equilibrium calculations were done by
minimizing Gibbs free energy using the predictive Soa-
veeRedlicheKwong method in AspenPlus
, after evaluating
against other equation of state based methods and discussing
about the simulation of the supercritical state. The aim was to
identify the operating conditions that maximize hydrogen
production from a mixture of water and glycerol. The effects
of reaction temperature and pressure as well as the glycerol
feed concentration have been studied for pure glycerol and
pretreated crude glycerol consisting mainly of glycerol and
methanol, by varying this latter from 10 to 30 wt%. The
reforming reactor and the wateregas shift reactor work at
isothermal condition.
From a thermodynamic point of view, and under equilib-
rium conditions, the best conditions to optimize hydrogen
production are 900  C and 1 mol % glycerol in the feed. By this
way, a hydrogen yield of about 95% for the pure glycerol and
97.2% for pretreated crude (20 wt% methanol) glycerol in the
reforming reactor are achieved. These values rise to 99.7% and
99.9% in the wateregas shift reactor, respectively. However,
compared to pure glycerol, the use of crude glycerol to produce
hydrogen gives a lower performance regarding with the molar
flow-rate of hydrogen produced in the reforming reactor due to
the lower number of atoms present in methanol, i.e., the
hydrogen production per mol of (pure or crude) glycerol is
higher for pure glycerol. The water to crude glycerol ratio is
a key factor to reduce the CO content in the WGS reactor, and
the hydrogen yield decreases and methane production rises as
the glycerol feed concentration increases, so a high water flow-
rate is required. The operating pressure does not affect the
results in the studied range (200e300 atm), and the analysis
shows that a suitable operation pressure may be about 240 atm.
For practical purposes, it is recommended to operate at
temperatures from 750 to 800  C, depending on the hydrogen
yield specified, since the glycerol conversion is total in all the
range. Operating at not too high temperatures reduces the
energy cost and extends the durability of materials. This is very
important since under operating conditions so severe (combi-
nation of high pressure and temperatures) the special mate-
rials required significantly increase the cost of the plant.
The next work will consist of a conceptual design of the
overall process including an energy and exergy analysis of
the SCW reforming of glycerol. Likewise, a facility is being
assembled to test the performance of this process. One of
the foreseeable features is that the catalyst will not be
strictly necessary. This is an important issue to be checked
since, so far, it is crucial to identify catalysts and design
reactors that maximize the yields of desired products and
minimize undesired by-products formed in series and/or
parallel reaction pathways. Thus, next the process will be
tested by a tubular reactor with and without using catalyst.
In addition, it will be assessed the effect of reaction time by
changing the feed flow-rate and performed studies on
chemistry kinetics.
Acknowledgment
This research is supported by the Science and Technology
Ministry of Spain under the research project ENE2009-13755,
as a Project of Fundamental Research inside the framework
of the National Plan of Scientific Research, Development and
Technological Innovation 2008e2011.
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