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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1

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Supercritical water gasification of biomass:

A stoichiometric thermodynamic model

Daniele Castello, Luca Fiori*

Department of Civil, Environmental and Mechanical Engineering, University of Trento, via Mesiano, 77, 38123,
Trento, Italy

article info abstract

Article history: Supercritical water gasification (SCWG) of biomass was studied by means of a stoichio-
Received 24 October 2014 metric thermodynamic model. Such approach is based on reaction equilibria and it allows
Received in revised form calculating the extent of the single reactions involved. A very simple model was proposed,
18 March 2015 involving only 6 components and 3 independent reactions. The model was validated
Accepted 24 March 2015 against literature experimental data for different feedstock and it was used to understand
Available online 17 April 2015 the influence of biomass and operating conditions. The analyses allowed calculating the
values of the reaction extent of water-gas shift (WGS) and CO methanation at equilibrium:
Keywords: a graphical approach was proposed in order to interpret the outcomes. Results showed that
Supercritical water gasification the influence of pressure is very limited. Moreover, it was observed that the maximum H2
Thermodynamic modeling production is linked to a parameter j, function of the H/C and O/C ratios of the feedstock.
Biomass Finally, considerations about the role of WGS and methanation in the production of H2
Stoichiometric model were traced.
Steam reforming Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Steam gasification reserved.

Nowadays, the preferred way to produce H2 is represented by

Introduction
Biomass is potentially the basis for the chemistry of
tomorrow. Indeed, it can be considered as the starting brick
for both energy generation and chemicals production [1].
Biomass could be thus regarded as the oil of the future. As
far as fossil resources become less available in the world,
biomass importance becomes more and more relevant.
Shortage in fossil resources, which is expected in the next
decades, will lead to a significant increase in the price of oil. It
can be thus foreseen that the interest for biomass utilization
would become even larger.
Biomass can also be an effective feedstock for the pro-
duction of H2, a clean energy vector for the future [2].
the steam reforming of methane [3], which is a fossil fuel.
Therefore, it causes net CO2 emissions in the atmosphere,
thus contributing to global warming. Vice versa, if H2 is pro-
duced from biomass, and the feedstock is grown and handled
in a sustainable way, this will reduce or even avoid net CO2
emissions in the atmosphere. Indeed, the carbon released by
biomass processing is the same carbon stored in the tissues of
living beings during their entire life. Producing H2 from
biomass would be an useful way to build a sustainable H2
economy [4].
One of the most promising technologies to valorize
biomass into gaseous fuels, and mainly into H2, is supercritical
water gasification (SCWG) [5,6]. Such process involves the re-
action of biomass with water at supercritical state, i.e. at

* Corresponding author. Tel.: 39 0461 282692; fax: 39 0461 282672.

E-mail address: luca.fiori@unitn.it (L. Fiori).
http://dx.doi.org/10.1016/j.ijhydene.2015.03.120
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
6772 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
temperature and pressure above 374.1  C and 22.1 MPa,
respectively. Water at supercritical state exhibits interesting
properties [7]. First of all, it shows thermo-physical properties
which are intermediate between those of a liquid and those of
a gas: high density, high transport coefficients. Moreover,
supercritical water is effective in dissolving many organic
compounds, thanks to its reduced polarity which makes it
similar to a non-polar solvent [5]. For all these reasons, in
SCWG a very homogenous and reactive environment is
established. In this way, reaction product yields are high and
some typical problems of traditional gasification can be
overcome, such as the formation of char and tar [8,9]. More-
over, since water is part of the process, through SCWG it is
possible to treat feedstock with a very high moisture content
(e.g. agricultural waste [10], sewage sludge [11], paper industry
byproducts [12], etc.), which can be hardly treated with other
thermo-chemical technologies. The environmental sustain-
ability of the process has been proved through life-cycle
assessment [13].
SCWG has been the subject of many studies in the litera-
ture, both experimental and numerical. Numerical studies
have mainly focused on thermodynamics modeling, which is
a very powerful tool to investigate over several aspects of the
process. The composition of the product gas, the amount of
energy required to run the process and the influence of the
operating conditions are just some of the questions that can
be answered through thermodynamics modeling [14]. There
are two possible approaches to thermodynamic equilibrium
modeling, according to the way the chemical system is
defined [15]. The first one is called non-stoichiometric and it
represents the most utilized class of models. The non-
stoichiometric approach relies on the minimization of Gibbs
energy. In this way, it is possible to calculate the equilibrium
composition of the system just imposing a list of possible
species expected at equilibrium and the initial system
composition. Non-stoichiometric modeling has the great
advantage of allowing calculating the equilibrium composi-
tion of the system without requiring the knowledge of the
reactions involved. For biomass, it represents an important
power point, since the exact reactions and the intermediates
involved are extremely difficult to know. In the literature,
there are several examples of studies making use of non-
stoichiometric models [16e19]. Such models were also uti-
lized along with commercial process simulators (e.g. Aspen
Plus), in order to obtain information about the economic
profitability of SCWG [20].
Conversely, the second approach to thermodynamic
equilibrium modeling, called stoichiometric, has not
received enough attention up to now. Stoichiometric
modeling relies on the definition of precise reaction mecha-
nisms, even if only at the macro level (i.e. it does not account
for instable chemical species and reaction intermediates). It
must be stated that, once all the independent chemical re-
actions have been identified, the two approaches are equiva-
lent, since they foresee exactly the same equilibrium
composition [14,21]. However, through the stoichiometric
approach it is possible to obtain a number of interesting out-
puts, for example the reaction extent of the single reactions
involved, allowing to obtain the reaction pathway favored by
thermodynamics. To our knowledge, such kind of elaboration
has never been carried out so far. The only model in the
literature dealing with a stoichiometric approach applied to
SCWG is represented by the work by Letellier et al. [22]. Here,
the authors presented a thermodynamic model based on 10
components and 7 reaction equilibria. The model has proven
quite effective in predicting the equilibrium composition of
the system. In a subsequent work by the same authors, the
model was also applied for an energy analysis of the process
[23]. However, such stoichiometric model was only utilized to
obtain the very same data that could be obtained from a non-
stoichiometric model. The added value of such class of
models, which is represented by the information about the
extent of the single reactions, was not presented.
The present work aims at investigating SCWG by means of
a non-stoichiometric model, in order to retrieve information
about the extent of the single reactions involved. The model
here proposed accounts for a very limited number of com-
ponents and reactions, in order to achieve the highest level of
simplification. In particular, the attention was focused on
water-gas shift (WGS) and CO methanation, which are the
key reactions taking place in the supercritical phase. A
graphical analysis was proposed for the interpretation of the
results. The influence of operating conditions and biomass
composition was discussed. Finally, considerations were
made about the conditions that maximize the production of
H2.
Model description and implementation
In this work, the following stoichiometric model is proposed,
based on a reduced number of chemical reactions. This simple
model is based on the assumptions that:
a) at equilibrium, all the incoming biomass is converted, thus
no biomass is found after the reaction;
b) at equilibrium, the only compounds which can be found
are water, hydrogen, methane, carbon monoxide and car-
bon dioxide.
These two assumptions can be reasonably justified by
referring to the state-of-art literature. Other thermodynamic
analyses of the SCWG process highlighted that no biomass is
found at equilibrium, even when feeding concentrations are
high and system temperature is low [16e18]. Moreover, the
previously cited compounds can be considered the only gasi-
fication products which are found in significant amounts
[16e18]. For completeness, evidence for such assumption will
be provided in Model validation and comparison.
In this model, biomass is schematized as a pseudo-
molecule whose formula is CHyOz. For sake of simplicity, the
stoichiometric index of C was always set equal to 1. As a
consequence, the stoichiometric indices y and z represent,
respectively, the hydrogen-to-carbon and the oxygen-to-
carbon atomic ratio in the considered biomass (y H/C;
z O/C).
The model includes a first reaction by which biomass is
converted into carbon monoxide and hydrogen by means of
water.
 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1 6773

y 8
CHy Oz 1  zH2 O/CO 1  z H2 (1) >
> 4xCO2 4xH2
2 >
> K2
>
> 4x CO 4xH2 O
>
>
>
>  
This equation is assumed to be completely shifted to the >
> 2
4xCH4 4xH2 O
>
> P
right (i.e. its equilibrium constant K can be considered to be >
> K3
>
< P o 4xCO 4x3H2
infinite). This means that no biomass is found at equilibrium.   (7)
After this reaction, the system is only composed of H2O, CO >
> Mtot xCO xCO2 xCH4 MC
>
>
>
>  
>
and H2. Other two stoichiometric independent reactions can > Mtot 2xH2 4xCH4 2xH2 O MH
>
>
be written to express the formation of CO2 and CH4. The >
>  
>
> M x 2xCO2 xH2 O MO
>
> tot CO
former is the water-gas shift (WGS) reaction, which expresses >
:
xCO xCO2 xCH4 xH2 O xH2 1
the equilibrium between CO and CO2:

CO H2 O/CO2 H2 (2) Where MC, MH and MO are the total number of moles of carbon,
hydrogen and oxygen present in the system. Such non-linear
The latter is the CO methanation reaction:
algebraic system was solved by using the numerical calculus
CO 3H2 /CH4 H2 O (3) software MatLab (The Mathworks, Inc.). The solution was
imposed to be non-negative. Such statement is fundamental
It can be observed that the number of equation (3) is the for a correct implementation of the problem, since it excludes
maximum number of independent reactions involving the those solutions which are mathematically possible but have
given compounds (6). As a consequence, the results of such no physical meaning.
model are equivalent to those obtained with the direct Gibbs Unlike reaction 1, which is assumed to be completely
energy minimization. shifted towards the products, both reactions 2 and 3 are
For both reactions 2 and 3, an equilibrium constant Ki can equilibrium reactions. This means that, depending on the
be defined, which is calculated by means of purely thermo- operating conditions (i.e. temperature, pressure and biomass
dynamic data: concentration), they can be more or less shifted towards the
  products.
Do G
Ki exp  (4) It is useful to refer to a and b, the reaction extents of re-
RT
actions 2 and 3, respectively. Such parameters reflect the
Such equilibrium constant can be related to the equilib- relative amount of CO reacted through each reaction. Both
rium composition of the system through: parameters assume the value 1 if all the CO in reactions 2 and
3 respectively is converted. Vice versa, their value is 0 if no CO
Y
N
n
Ki aj j (5) is converted through those reactions (and thus equilibrium is
j1 completely shifted towards the reactants). From a mathe-
Where aj is the activity of the j-th species, to the power of its matical point of view, the values of a and b are equal to the
own stoichiometric coefficient (negative for the reactants). number of moles of CO2 and CH4, respectively:
The activity is defined as:
a Mtot xCO2 (8)
fj 4j Pxj
aj o (6) b Mtot xCH4 (9)
fjo P

Where xj is the molar fraction of the j-th species and 4j is its
fugacity coefficient, which accounts for the non-ideality of the
gaseous mixture.
In order to calculate 4j, Peng-Robinson equation of state
(EoS) was used [24], along with van der Waals mixing rules to
account for the presence of a mixture rather than a pure
compound. The procedure that was utilized in order to
calculate 4j according to the Peng-Robinson EoS was detailed
in a previous work by our group [18]. To achieve an even
higher grade of simplification, the model was also run by
using the ideal gas EoS. In this case, fugacity coefficients are
all equal to 1.
The problem is made up of 6 unknowns which are repre-
sented by the molar fractions of the 5 gaseous species
involved in the model, plus the total number of gaseous moles
Mtot. Besides chemical equilibria of reactions 2 and 3, the
model also involves three equations for the elemental balance
of carbon, hydrogen and oxygen respectively and a congru-
ence equation, which states that the sum of the molar frac-
tions xj must be equal to 1.
The final system can thus be written in the following way:
Indeed, such two molecules are only produced by reactions
2 and 3 and, thus, they specifically identify those reactions. It
is now possible to write an overall reaction for SCWG (Eq. (10)),
by combining reactions 1, 2 and 3 together. Eqs. (2) and (3)
must be taken into account each multiplied by its own reac-
tion extent.
CHy Oz 1  z a  bH2 O/1  a  bCO
h
y i (10)
1z a  3b H2 aCO2 bCH4
2
Results and discussion
In the present section, the main results of the model runs are
presented. The model is first validated against experimental
literature data and then a graphical interpretation of the re-
sults is provided, which is useful to highlight the dependence
of the equilibrium composition on the different biomass and
reaction conditions.
6774 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1

Model validation and comparison

Table 1 e Root mean square deviation (RMSD) between
the experimental data by Byrd et al. [25,26] and the model
The model was first validated against the experimental data predictions obtained by using Peng-Robinson and ideal
obtained by Byrd et al., who performed the SCWG of glycerol gas EoS.
[25] and ethanol [26] in the presence of a Ru/Al2O3 catalyst. Ethanol Glycerol
The model was run with both Peng-Robinson and ideal gas
Peng-Robinson Ideal gas Peng-Robinson Ideal gas
EoS, with the aim of comparing such two different ap-
proaches. The results are presented in Fig. 1. H2 0.0359 0.0325 0.0227 0.0250
CO 0.0315 0.0301 0.0366 0.0345
Fig. 1a and b testify that the mathematical model is able to
CH4 0.0280 0.0282 0.0333 0.0315
predict the experimental data in a very satisfactory way. The
CO2 0.0205 0.0196 0.0442 0.0455
production trend of all the main permanent gases (H2, CO,
CH4, CO2) was correctly predicted. The accuracy of the fitting
was evaluated in terms of the root mean square deviation temperature is high, the differences between Peng-Robinson
(RMSD): Table 1. and ideal gas EoS tend to be barely visible. When operating
In Table 1, it can be noticed that the value of the RMSD is at lower temperatures, i.e. around 400e500  C, the two EoS
very low for both the EoS utilized. Indeed, in both cases the result in sensibly different results, especially for H2 and CH4.
molar fractions predicted by the model do not differ from the Differences are more evident at low feed concentrations
experimental data by more than 0.05. This testifies that the (Fig. 1c) than at high ones (Fig. 1d). At a feed concentration of
proposed model, though very simplified with respect to pre- 5 wt. % (Fig. 1c), H2 molar fractions differ for 0.12 at T 400  C.
vious literature works, is able to predict the system output in a Such large differences can be due to the lower accuracy of
very satisfactory way. As far as the two EoS are concerned, the the ideal gas EoS as the critical point is approached. Whereas
differences are minimal and both model outputs are affected at high temperatures the ratio of the fugacity coefficients in
by a similar error. reactions 2 and 3 (see Eq. (7)) tends to 1 also with the Peng-
However, it must be pointed out that the experimental data Robinson EoS, at lower temperatures such condition is no
considered for the comparison were obtained at a relatively longer respected. As a consequence, it should be concluded
high temperature. As it is witnessed by Fig. 1c and d, when the that the Peng-Robinson EoS is preferable, since it can be

Fig. 1 e Model validation and comparison between ideal gas and Peng-Robinson EoS. Dots: experimental data; solid lines:
model output using Peng-Robinson Eos; dashed lines: model output using ideal gas EoS. (a) Validation against the data of
Byrd et al. [25] for glycerol (T 800  C, P 24.1 MPa); (b) Validation against the data of Byrd et al. [26] for ethanol (T 800  C,
P 22.1 MPa); (c) Comparison between model output varying the temperature (glycerol at 25.0 MPa and feed concentration
of 5 wt. %); (d) Same at a glycerol concentration of 30 wt. %.
 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
effective in predicting the system behavior over all the
investigated reaction conditions. Therefore, the subsequent
calculations are performed by means of such EoS.
The results of the present model can be effectively
compared with those of much more complicated models. To
this purpose, the model was compared with a non-
stoichiometric model presented in a previous work of our
group [18], which included 22 species. Though it takes into
account only 6 components, the present stoichiometric model
is able to foresee exactly the same outcomes as the non-
stoichiometric model. Fig. 2 clearly shows that the results of
both models are practically identical. Using only 6 compounds
rather than 22 does not affect the results. Indeed, the adoption
of a larger (i.e. more complete) model could be justified when
minor or trace concentrations of certain compounds are of
interest, e.g. for pollutants or minerals. If only macroscopic
concentrations are needed, no difference can be found be-
tween the simplified and a larger model. Moreover, it must be
pointed out that the mathematics behind a non-
stoichiometric model is much more complicated than that
involved in a stoichiometric model. The former relies on the
solution of a constrained optimization problem, while the
latter is based on the solution of a non-linear system of alge-
braic equations. Therefore, since it allows obtaining the same
results with a reduced computational effort, the proposed
model represents an effective and simple tool to describe
SCWG and other similar processes occurring at lower pres-
sure, like steam reforming and steam gasification.
Stoichiometric constraints and graphical analysis
An analysis of the overall SCWG reaction presented in Model
description and implementation (Eq. (10)) allows obtaining
precious information about the stoichiometric constraints of
the process. Two constraints can be easily introduced. In
SCWG, indeed, CO and H2 are always products and never
Fig. 2 e Parity plot: comparison between the results of the
present stoichiometric model and the results of the non-
stoichiometric model by Castello and Fiori [18]. The model
was run at the experimental conditions of the two works
by Byrd et al. [25,26].
6775
reactants. As a consequence, their stoichiometric coefficient
in Eq. (10) must always be equal to or higher than 0. With some
calculations, from the stoichiometric coefficient of CO it can
be obtained:
b1a (11)
And from that of H2:
1
y 
b 1z a (12)
3 2
Consider a plane in which the axes are represented by a
and b: Fig. 3. The inequalities presented in Eqs. (11) and (12)
identify a region of such plane, whose limits are represented
by the straight lines u and v in Fig. 3. The couples (a, b) lying on
line u represent the points corresponding to a null production
of CO. Each parallel to u represents the points characterized by
the same production of CO. Similarly, line v represents the
points having a null production of H2, and its parallels repre-
sent the points with the same production of H2. Unlike line u,
which is independent on the actual biomass, line v changes in
dependence of the specific biomass. The coordinate of its
intersection point with the vertical axis (point B) depends on
the specific organic molecule, i.e. on the values of y and z,
while its slope is constant at the value of 1/3.
The intersection between lines u and v (i.e. point C) repre-
sents the point at which neither CO nor H2 are produced. As a
consequence, the only gaseous products of the reaction are
CH4 and CO2. In particular, such point corresponds to the
maximum production of CH4, since it is characterized by the
highest value of b. Interestingly, the maximum extent of
methanation does not occur in the absence of WGS. Indeed,
though WGS consumes some CO (which is also a reactant for
methanation), WGS produces H2, which is needed by metha-
nation. Point C represents the tradeoff between the two re-
actions which maximizes methanation.
The other vertices of the trapezoid also have an important
meaning. Vertex D represents the point where neither CO nor
CH4 are produced: indeed, b 0. As a consequence, here the
Fig. 3 e The a-b plot and its relevant points.
6776 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
only reaction is WGS and the products are H2 and CO2 only.
Moreover, this is also the point where such two permanent
gases reach their maximum production. Vertex A, i.e. the
origin of the axes, is characterized by neither WGS nor
methanation and it represents the point where only H2 and CO
are produced, CO at its maximum extent. Finally, vertex B
represents the point where only CH4 and CO are produced.
All the possible couples (a, b), that is each result of the
mathematical model, must lie inside the trapezoid ABCD,
which represents the solution space. Next Sections show how
biomass composition and process conditions influence the
model outputs and thus the location of the couples (a, b) in the
solution space.
The influence of process parameters and feedstock
According to the graphical construction presented in Stoi-
chiometric constraints and graphical analysis, the model was
run in order to observe how the points with coordinates (a, b)
e model outcomes e move within the solution space varying
the process parameters (temperature, pressure and biomass
concentration). The results of such calculations are reported
in Fig. 4. In each of the four plots, a couple of process pa-
rameters was varied, holding the third at a constant base
value. The range of variation of all parameters as well as their
Fig. 4 e Effect of the operating conditions on model outputs. (a) Temperature and feed concentration (P 25.0 MPa); (b)
Magnification of (a) with the indication of temperatures and feed concentrations; (c) Temperature and pressure (X 15 wt.
%); (d) Pressure and feed concentration (T 600  C). The range of variation of the operating conditions is reported in Table 2.
Feedstock: Microalga Spirulina.
Table 2 e Range of variation of the process parameters
utilized in the simulations.
Parameter Range Base value

Temperature [ C] 400e1000 600
Pressure [MPa] 22.0e35.0 25.0
Feed concentration [wt. %] 5e95 15
base value are summarized in Table 2. The curves repre-
senting the points obtained at the same temperature (iso-
therms), the same pressure (isobars), and the same biomass
concentration (iso-concentrations) were traced. Microalga
Spirulina was adopted as the feedstock for all the simulations.
Its composition (pseudo-formula) was reported in Table 3. It
must be stated that some of the process conditions hereby
analyzed are quite far from practical SCWG applications, as
they include very high values of feedstock concentration,
which may sound unrealistic. However, they were included
in the analysis in order to show a more complete trend of
results.
In all cases, the calculated points fall inside the trapezoid
ABCD, as it was theoretically expected. Notably, the only plots
where the solution space is filled to a large extent are in Fig. 4a
and b, where pressure was kept constant and T and X were
varied. Actually, Fig. 4b is a mere magnification of Fig. 4a,
 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
Table 3 e e Biomass stoichiometric factor j, molecular weight of the pseudo-mole and maximum H2 production for
different substrates.
Substrate Pseudo-formula J [e]
Glucose C1H2O1 0 30.00
Phenol C1H1O0.167 0.667
Glycerol C1H2.667O1 0.667
Paper residue C1H1.569O0.843 0.117
Sewage sludge C1H1.721O0.442 0.837
Microalga Spirulina C1H1.866O0.589 0.688
Oak wood C1H1.455O0.674 0.107
Pine wood C1H1.494O0.660 0.174
Grape marc C1H1.265O0.427 0.411
provided for ease of observation. Isotherms and iso-
concentrations form a network of lines. Isotherms originate
from the bottom-right corner of the plot and tend to line u
when temperature decreases. For low biomass concentra-
tions, WGS tends to its maximum extent, while CO metha-
nation is minimal, regardless of the system temperature.
Therefore, the maximum H2 molar productions are reached by
operating at very low biomass concentrations. Isotherms at
low temperatures present a steep trend, which tends to make
them parallel to line u. This implies that, for low-temperature
SCWG, increasing biomass concentration affects the extent of
both WGS and methanation in a similar way. As temperature
increases, the slope of the isotherms decreases. As a conse-
quence, at high temperatures, increasing the concentration
has limited effects on the extent of methanation, while it
strongly influences the extent of WGS.
If iso-concentrations are analyzed, it can be observed how,
for low temperatures, they tend to be originated from point C,
that is the intersection between u and v. Indeed, very low
temperatures favor the production of CH4, which is maximum
at point C (see Stoichiometric constraints and graphical
analysis). The trend of iso-concentrations is in most cases
approximately vertical. Therefore, at fixed biomass concen-
tration, temperature plays a stronger effect on the extent of
methanation than on the extent of WGS. The effect of tem-
perature on WGS becomes remarkable for very low biomass
concentrations. It can be observed that each iso-
concentration shows a maximum in the value of a. This
issue will be detailed in Maximizing H2 production.
When observing Fig. 4c and d, where pressure is one of the
varied parameters, the situation is completely different.
Whereas in Fig. 4a and b the area of the trapezoid was covered
by the calculated points to a significant extent, in both Fig. 4c
and d the location zone of the calculated points is extremely
limited.
Actually, in Fig. 4c it is only possible to distinguish the
isobars, having an almost vertical trend. Such curves are very
close to one another, and they look as a single line. Isotherms,
which connect those points obtained by varying the pressure,
are consequently very short segments. A similar situation can
be observed in Fig. 4d, where pressure and biomass concen-
tration were varied. Again, the calculated points are located in
a narrow region of the solution space, corresponding to all the
very close isobars. By looking at the mathematical formula-
tion of the model, it can be observed that pressure is only
active in influencing methanation, which is the only reaction
6777
Molecular wt. [g/mol] Max. H2 production [g/kgfeedstock]
133.3
15.67 297.9
30.67 152.2
27.06 143.5
20.79 232.6
23.29 201.3
24.24 169.4
24.05 173.5
20.10 219.5
implying a variation in the total number of moles. However,
the overall effect of pressure is very limited.
Such analyses reveal that, of all the parameters which are
utilized, only temperature and biomass concentration play
an appreciable role. The influence of pressure is very limited
and therefore it will be neglected for the subsequent
analyses.
The composition of the feedstock is a main parameter of
the model. In Fig. 5, the a-b plots for four different substrates
are depicted. The values of y and z of the biomass pseudo-
molecules were determined according to the dry ash-free
composition reported by the database Phyllis, a large collec-
tion of biomass data powered by ECN, Netherlands [27]. Data
can be found in Table 3.
As it was observed in Stoichiometric constraints and
graphical analysis, the composition of the biomass is the
only parameter that determines the shape of the solution
space. Indeed, line v is dependent on the actual composition
of the biomass, through the values y and z. By re-arranging Eq.
(12), such dependence can be linked to a single parameter,
here referred as stoichiometric factor j and defined as:
j y  2z (13)
The value of j determines the shape of the a-b plot. Evi-
dence of this is found by comparing the different plots in
Fig. 5. Paper residue (Fig. 5a), sewage sludge (Fig. 5b), and
phenol (Fig. 5c) show different stoichiometric constraints, as
they have different values of j. Conversely, when phenol is
compared to glycerol (Fig. 5d), the stoichiometric constraints
are the same. In this case, indeed, both substrates present the
same value of j.
The similarities between the various plots are not limited
only to the stoichiometric constraints. Indeed, if Fig. 5c and
d are compared, also the isotherms appear to be coincident.
This because the equilibrium constants Ki depend only on
temperature. Therefore, when the stoichiometric constraints
of two substrates are equal, the isotherms are necessarily
coincident. Conversely, iso-concentration lines in Fig. 5c and
d do not show exactly the same trend. For glycerol, which has
a higher pseudo-molecular weight (i.e. the weight of the
pseudo-molecule, Table 3), the iso-concentration lines are
shifted towards the right.
Since isotherms coincide, in a region of the solution space
where the iso-concentrations show low variability and thus
are very close, both substrates tend to give the same results.
6778 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1

Fig. 5 e a-b plots for different substrates at 25.0 MPa: (a) Paper residue; (b) Sewage sludge; (c) Phenol; (d) Glycerol. The range
of variation of T and X is reported in Table 2.

This is the case of low temperatures, where phenol and

4j
glycerol tend to give the same gas composition at equilibrium. Ymass (15)
MW

Maximizing H2 production The maximum production of H2 is thus a tradeoff between

The stoichiometric factor j is linked to the production of H2
per pseudo-mole of feedstock. Indeed, from Eq. (10) the
number of moles of H2 which can be produced per pseudo-
mole of feedstock can be calculated:
 
j retically achievable H2 yields that can be obtained (i.e. when
Ymol 1 a  3b
2 a 1 and b 0). The system tends to such production for low
For each feedstock, the maximum H2 production is achieved
when a 1 and b 0, corresponding to both low biomass
concentration and high temperature. At such conditions, j is
the only parameter that matters: the higher is j, the higher Ymol.
As a consequence, two substrates with the same value of j
show the same maximum production of H2 per pseudo-mole of
feedstock: this is the case, for example, of phenol and glycerol.
Importantly, it must be pointed out that the value of Ymol
refers to a pseudo-molecule, which does not exist in reality. In
order to get a value with practical meaning, the production of
H2 per unit mass must be taken into account. For its calcula-
tion, the previous value should be divided by the molecular
weight of the pseudo-molecule MW and multiplied by the
molecular weight of H2, thus obtaining the maximum mass
yield of H2 per unit mass of feedstock Ymass:
j and the weight of the feedstock pseudo-molecule: the
former must be as high as possible, the latter must be as low
as possible.
In Table 3, the calculation of j, molecular weight and
maximum H2 production was reported for different sub-
strates. Such values of Ymass represent the maximum theo-
(14)
values of biomass concentration and high temperatures, i.e.
around point D of the a-b plot.
Apart from the maximum achievable production (point D),
it is interesting to determine the maximum H2 yields that can
be obtained at equilibrium at each feed concentration.
According to Eq. (14), for a given biomass (i.e. once fixed the
value of j), the production of H2 depends on the values of a
(reaction extent of WGS) and b (reaction extent of methana-
tion): the former has a positive effect, while the latter has a
negative effect. To achieve the highest H2 production, a must
be maximized while b must be minimized. Now, focus on a
single iso-concentration line in Fig. 5 or Fig. 4b. For increasing
values of the temperature, b is always decreasing, thus an
increase in temperature makes the extent of the methanation
reaction to decrease. For increasing values of the temperature,
 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
Fig. 6 e (a) Maximum H2 production at equilibrium and maximum value of a and (a e 3b) as a function of feed concentration
for glycerol (P 25.0 MPa); (b) Temperatures at which maximum value of a and (a e 3b) occur, as a function of feed
concentration.
conversely, a increases at first and then it decreases, after
reaching a maximum point.
The occurrence of such maximum is due to two competing
factors. An increase in temperature highly disfavors metha-
nation (and correspondingly b decreases), which is highly
exothermic, thus more CO and H2 are available in the system.
When the excess of water is very high (i.e. for low feedstock
concentrations), most of the CO is converted by WGS which,
however, is exothermic too, thus disfavored by an increase in
temperature. At lower temperatures, the former effect pre-
vails (i.e. a increases due to the higher amount of available CO)
while at higher temperatures it is overcome by the latter (i.e. a
decreases due to the exothermicity of WGS). Notably, the
temperature at which such maximum occurs decreases as
biomass concentration increases. There is no maximum point
for a when high feedstock concentrations are involved.
In Fig. 6a the values of the maximum production of H2 at
equilibrium and of the maximum a and a e 3b as a function of
feed concentration are reported. In Fig. 6b, the temperatures
at which such values are reached are shown. Notably, the
maximum production of H2 at equilibrium coincides with the
maximum value of the function (a e 3b) according to Eq. (14).
Consequently, the temperature at which the maximum pro-
duction of H2 at equilibrium is achieved coincides with the
temperature which maximizes a e 3b and which is reported in
Fig. 6b. It is worth pointing out that maximum here simply
refers to the largest value of the function achieved at each feed
concentration, which is not necessarily a maximum from the
mathematical point of view (i.e. a point where the first deriv-
ative of the function is null).
Operating at low feed concentration is theoretically ad-
vantageous, since the specific yields of H2 are maximal and
they are achieved at lower temperatures. Moreover, looking at
Fig. 6b, the temperatures at which the maximum H2 yield and
the maximum extent of WGS occur tend to be coincident.
Thus, at low feed concentration most of the H2 production can
be attributed to WGS (i.e. a z 1 and b z 0, Fig. 6a).
Despite the advantages of working at low concentrations,
real applications of SCWG need reasonable feed
6779
concentrations, usually in the range of 15e25 wt. %, to ensure
the economic feasibility of the process [20]. At such condi-
tions, the maximum achievable specific H2 productions are
lower (Fig. 6a) and, at the same time, they are obtained at
much higher values of temperature. In Fig. 6b it can be
observed that, at increasing concentrations, the temperature
at which the maximum H2 yield occurs is increasingly higher
than the temperature at which the maximum WGS extent is
achieved. From this, it can be stated that most of the H2 pro-
duction obtained at high feed concentrations is caused by the
suppression of methanation (the term -3b in Eq. (14)), rather
than by an enhancement of WGS.
Therefore, in order to achieve the maximum yields of H2, it
is necessary to operate at a temperature higher than the
temperature corresponding to the maximum extent of WGS.
Such further temperature increase is thus only required to
suppress methanation, since it cannot have any effect on WGS
(actually, its effect is even detrimental on WGS). Methanation
is indeed an exothermic reaction, thus it is disfavored at high
temperature. In order to maximize H2 production while mini-
mizing the process temperature, a possible way could there-
fore be to operate the SCWG reactor at the temperature which
maximizes WGS, while attempting to suppress methanation in
other ways. One possibility could be to supply CH4 to the
reactor, in order to shift the equilibrium of methanation to-
wards the reactants. A closed loop could be envisaged, with the
separation of CH4 from the products stream and its re-
injection into the SCWG reactor. Further research is needed
in order to clarify the viability of this solution on actual plants.
Conclusions
In the present paper, a stoichiometric model for the SCWG of
biomass was presented. Such model was able to predict the
thermodynamic behavior of the reacting system by relying on
an extremely reduced set of equations: only 3 equations and 6
components. From the computational point of view, such
model can be very advantageous. Unlike non-stoichiometric
6780 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 4 0 ( 2 0 1 5 ) 6 7 7 1 e6 7 8 1
approaches, which are based on the solution of a minimiza-
tion problem, here the mathematics is reduced to the solution
of a non-linear algebraic system, which can be achieved with
limited computational effort. The calculated results are
practically coincident with those obtained with other models
based on Gibbs energy minimization. It was decided to adopt
Peng-Robinson EoS to model the supercritical phase. Howev-
er, it has been demonstrated that the utilization of the ideal
gas EoS could lead to acceptable results at high temperatures
and low feed concentrations, thus achieving a further
simplification.
The model was able to provide information about the
relative importance of WGS and methanation, which are the
two main reactions taking place in the supercritical phase.
The treatise was carried out by means of a graphical approach
(a-b plot) that helped understanding the influence of the
process parameters on the model outputs. It was then possible
to state that only temperature and feed concentration play a
significant role, while the influence of pressure is very limited.
As far as the feedstock composition is concerned, it was
highlighted the role of the factor j, which relates the ratios H/
C and O/C. Different organic molecules with the same value of
j show the same maximum theoretical production of H2 per
pseudo-mole. The maximum production of H2 per unit mass
of feedstock is a tradeoff between j and the pseudo-molecular
weight. In order to achieve the maximum H2 production, the
former should be maximal, while the latter minimal.
The stoichiometric approach was also effective in clari-
fying the relative contribution of WGS and methanation to H2
production. It was pointed out that the temperature corre-
sponding to the maximum extent of WGS reaction is lower
than the temperature at which the maximum H2 production is
achieved. Such higher temperature is thus needed only to
suppress methanation. Finding strategies to inhibit metha-
nation would thus increase the H2 yields while allowing to run
the SCWG reactor at reduced operating temperatures.
Nomenclature
y atomic ratio H/C, e
z atomic ratio O/C, e
K equilibrium constant, e
R universal gas constant, J mol1 K1
T temperature, K
a activity, e
f fugacity, MPa
P pressure, MPa
x molar fraction, e
M number of moles, mol
MW molecular weight, g/mol
X feedstock concentration in the feed, wt. %
Y maximum yield of H2, e
N number of components, e
Greek symbols
4 fugacity coefficient, e
n stoichiometric coefficient, e
a reaction extent of WGS, e
b reaction extent of CO methanation,
j stoichiometric factor, e
Subscripts and superscripts
i i-th reaction
j j-th component

standard
tot total
mass mass
mol molar
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