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Bioresource Technology 102 (2011) 75747582

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Supercritical water gasication of biomass: Thermodynamic constraints


Daniele Castello, Luca Fiori
Civil and Environmental Engineering Department, University of Trento, Via Mesiano 77, 38123 Trento, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, the supercritical water gasication (SCWG) of biomass is analyzed with a view to
Received 9 March 2011 outlining the possible thermodynamic constraints that must be taken into account to develop this new
Received in revised form 6 May 2011 process. In particular, issues concerning the formation of solid carbon and the process heat duty are dis-
Accepted 8 May 2011
cussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model,
Available online 14 May 2011
based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs
at high biomass concentrations, with a strong dependence on biomass composition. As regards the pro-
Keywords:
cess heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small
Supercritical water gasication
Thermodynamic modeling
amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating
Energy analysis value of the syngas produced.
Biomass 2011 Elsevier Ltd. All rights reserved.

1. Introduction technologies are based on the partial oxidation of biomass, i.e. a


reaction where oxygen is supplied below the stoichiometric
The development of renewable energy sources in order to face amount. As a result, a gaseous mixture whose main compounds
the worlds future problems is acquiring growing importance on are H2, CO and CO2 is produced. An alternative solution is that of
account of several factors. First of all, a signicant shortage of fossil processing biomass through steam, thus achieving a steam reform-
fuels (oil, gas, and carbon) is foreseen for the next few decades as a ing reaction. In this case, H2 and CH4 are produced in higher
result of growing worldwide demand, boosted by developing coun- amounts, although the process requires large quantities of energy
tries. Secondly, fossil fuels are located to a great extent in politi- (Bridgwater, 2003). Other options have been proposed, for instance
cally and socially unstable regions, which makes their exports the usage of an airCO2 mixture as gasifying agent (Hurley et al.,
subject to uctuations in prices and supply. Finally, global warm- 2010).
ing issues, mostly related to CO2 releases in the atmosphere caused Anyway, traditional gasication technologies have encountered
by thermoelectric power plants and, more generally, by combus- a number of major difculties hampering their development. First
tion plants utilizing fossil fuels, have called on many national gov- of all, the quality of the product gas is usually low, since it is con-
ernments to look for alternative and more environmental-friendly taminated by impurities like char and tar. Therefore, expensive
ways to produce energy. purication operations are needed to achieve the required quality
In this context, biomass can be considered an effective source of standard (Hasler and Nussbaumer, 1999). Moreover, traditional
renewable energy. Biomass is renewable by denition and it can be gasication technologies require dry biomass, to avoid excessive
seen as an alternative way to store solar energy by using vegetal drying costs.
tissues. Biomass is thus CO2 neutral: the CO2 released with its com- Supercritical water gasication (SCWG) is a possible solution to
bustion (or possibly partial oxidation) derives from the carbon the these issues. Owing to the unique properties of water at supercrit-
plant stored in its tissues throughout its life. Unlike fossil fuels, bio- ical state (i.e. temperature and pressure higher than 375 C and
mass is more evenly distributed throughout the world. Therefore, 221 bar, respectively), extremely fast kinetics can be achieved, thus
it also implies geopolitical advantages. Among the different tech- avoiding the formation of tar and char and signicantly improving
nologies proposed for biomass conversion into energy, gasication the product gas quality. To this regard, Chuntanapum and Matsum-
is one of the most promising (Bridgwater, 2003; Zhang et al., 2010), ura (2009), who performed steam gasication of 5-HMF (a precur-
as it provides a gaseous product which can be directly burnt in en- sor of tar), highlighted that char particles form under subcritical
gines or turbines to produce electrical power. Standard gasication conditions but not in the supercritical state. Moreover, wet and
low-quality biomass can be effectively converted into gas
Corresponding author. Tel.: +39 0461 282692; fax: +39 0461 282672. (Matsumura et al., 2005), paving the way to the usage of large
E-mail addresses: daniele.castello@ing.unitn.it (D. Castello), luca.ori@ing. amounts of residual and waste materials. Literature reports on
unitn.it (L. Fiori). SCWG of sawdust, cornstarch, potato-starch and potato waste

0960-8524/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2011.05.017
D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582 7575

Nomenclature

A dimensionless form for a T temperature (K)


a PengRobinson attraction parameter (N m4 mol2) ~
V molar volume (m3 mol1)
B dimensionless form for b x molar fraction
b PengRobinson repulsion parameter (m3 mol1) Z compressibility factor

b term in PengRobinson EoS (m3 mol1)
cp isobaric heat capacity (kJ mol1 K1) Greek symbols
E matrix whose elements are gij u fugacity coefcient
f fugacity (Pa) l chemical potential (kJ mol1)
G Gibbs free energy (kJ mol1) gij binary mixture parameter for packing of unlike compo-
DH enthalpy change (kJ mol1) nents
HHV high heating value (kJ kg1) x acentric factor
kij binary mixture parameter for intermolecular interac-
tions Subscripts and superscripts
K matrix whose elements are kij 0 standard
N number of components c critical
n number of moles (mol) f formation
P pressure (Pa) m mixture
q1,..., q5 coefcients for cp calculation x stoichiometric index for carbon
r Pearsons correlation coefcient y stoichiometric index for hydrogen
R universal gas constant (J mol1 K1) z stoichiometric index for oxygen
DS entropy change (kJ mol1 K1) w stoichiometric index for nitrogen

(Antal et al., 2000), fruit shells (Demirbas, 2004), vinasses (Garca It was successfully applied in a study by Tang and Kitagawa
Jarana et al., 2008), and plant stalks (Yanik et al., 2007). (2005) where PengRobinson equation of state (EoS) was used to
So far SCWG has not been investigated extensively. Most of the predict the behavior of a supercritical mixture. Their analysis
studies have focused on experimental activities, mainly analyzing showed that high temperature, low pressure and low concentra-
the product gas composition for different feedstock by using small tion of biomass in the feed are the ideal conditions for hydrogen
laboratory devices (Antal et al., 2000; Taylor, 2003; Yanik et al., production through SCWG, in good accordance with experimental
2007; Byrd et al., 2008). A certain number of studies have also been data. A similar approach was adopted by Yan et al. (2006), who
devoted to the development of a catalyst in order to improve the used Duans EoS, which is considered more effective when dealing
SCWG process by reducing its energy needs and increase the selec- with supercritical mixtures. In this work, the authors also intro-
tivity towards hydrogen. An interesting review on this subject can duced a carbon conversion efciency coefcient to take into ac-
be found in Guo et al. (2010). count that equilibrium is not completely achieved in practice. As
So far only few works have been devoted to the physicmathe- a result, the conversion of the feedstock is not complete even after
matical modeling of the SCWG process, and most of them have fo- a long residence time. Another similar approach is that of Voll et al.
cused on thermodynamics. In this eld, two main approaches can (2009), who implemented a simplied model in order to overcome
be identied: stoichiometric and non-stoichiometric. The stoichi- some computational difculties and improve reliability. In all these
ometric approach is based on reaction equilibria. In other words, works, anyway, only one-phase (the supercritical phase) is consid-
a certain number of independent reactions involving the different ered and the energy requirements of the process are not analyzed.
species are considered. Calculations are then performed in order In the present work, a non-stoichiometric, two-phase model for
to nd the equilibrium among the reactions examined. This ap- SCWG is developed and implemented. This new model is able to
proach has the advantage of making the contribution of each reac- predict the system equilibrium composition not only considering
tion easily identiable. On the other hand, the reactions involved in the supercritical phase, but also the possibility for a solid phase
the conversion of biomass have to be known in advance. This ap- to form. This enables to foresee the formation of solid carbon
proach was implemented in the work of Letellier et al. (2010), among the reaction products. Another innovative aspect is that
where a system consisting of a SCWG reactor and an atmospheric biomass is not modeled just as a compound made of carbon, hydro-
pressure separator was modeled, taking into account seven inde- gen and oxygen, but nitrogen is also considered, thus allowing for
pendent reactions. In a subsequent work (Marias et al., 2011) the the occurrence of NOx compounds.
same research group applied the same model in order to study By means of this model, the conditions leading to the formation
the energy features of the process. The authors concluded that, of solid carbon were investigated as a function of the different pro-
when an oxidizing agent is fed to the reactor, an autothermal cess parameters (temperature, pressure, biomass concentration,
operational regime can be obtained without any external energy and biomass typology). An interesting issue is that of energy impli-
input to the system. cations, and thus the calculation of the process heat duty, which is
The other family of methods is called non-stoichiometric. Here a fundamental piece of information to state the real protability of
no reactions have to be dened, but the equilibrium composition is SCWG. In this sense, this work is the rst one delivering an energy
calculated according to Gibbs free energy minimization. In order to analysis by means of a non-stoichiometric model.
apply this family of models, the species expected in the products
need to be dened. Subsequently, the distribution of the products 2. Model description
enabling to reach the minimum value of Gibbs free energy is calcu-
lated. Although no reference to real reactions is made, this ap- The thermodynamic model proposed here is based on Gibbs
proach has the great advantage of being extremely exible and free energy minimization. This condition implies that the system
preventing that important reactions in the scheme are neglected. has reached an equilibrium state.
7576 D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582

Gibbs free energy of the system (G) can be calculated as the sum Thus, a third grade polynomial is obtained:
of each components chemical potential (li) multiplied by the   !
2
same components number of moles (ni): bP 2 aP bP b P2
Z3  1  Z  2  3 Z
X
N RT R2 T 2 RT R2 T 2
G ni li 1 !
2 2 3
i1 abP b P2 b P3
   0 10
The chemical potential is a function of temperature and pres- R3 T 3 R2 T 2 R3 T 3
sure, according to:
Solving Eq. (10) for Z, three solutions are obtained. When two
f phases are present, all the solutions are real. The minimum value
li T; P l0;i T RT ln i 2
is referred to the liquid phase and the maximum value to the
f0;i
gaseous phase; the middle value has no physical meaning. Above
l0,i is the chemical potential under standard pressure condi- the critical point, only one value is physically meaningful.
tions (101,325 Pa). It can be calculated as a function of enthalpy To deal with a mixture, rather than a pure compound, van der
and entropy of formation, which are only dependent on tempera- Waals binary mixing rules were introduced. These rules enable
ture, through the following formula: to calculate am and bm, which are the a and b parameters appearing
Z T Z T in Eq. (10) but with reference to a mixture of N components, each
C p;i T
l0;i T DH0f ;i C p;i TdT  T DS0f ;i  T dT 3 having the molar fraction x, in the following way:
298 298 T
In order to calculate the isobaric heat capacity cp, the NASA X
N X
N

polynomial formula was adopted: Eq. (4) (McBride et al., 1993). am xi xj aij 11
i1 j1
For each chemical species, this formula foresees two sets of ve
coefcients, one for the low temperature range (i.e. up to 1000 K)
X
N X
N
and another for the high temperature range (i.e. from 1000 to bm xi xj bij 12
6000 K). The generic formula can be expressed as: i1 j1

cp;i
q1 q2 T q3 T 2 q4 T 3 q5 T 4 4 where:
R
p
Coefcients q1,..., q5 for a large number of compounds can be aij 1  kij ai aj 13
found in McBride et al., 1993.
The second term after the equal sign in Eq. (2) takes into ac- bi bj
bij 1  gij 14
count the dependence on pressure by introducing the fugacity of 2
the i-th component, which is a state variable with units of pressure Parameters kij and gij are called interaction parameters and ex-
and is dened as: press the interaction between species i and j. They can be seen as
fi Pui xi 5 the elements of matrices K and E, which are symmetrical and have
null elements on the diagonal.
Actually, Eq. (2) considers the ratio between the fugacity of the Elements ki,j in matrix K were calculated according to Poling
i-th component in the mixture (fi) and the fugacity of pure compo- et al. (2007):
nent i at standard pressure conditions (f0,i; f0,i = P0). q
Term ui is called fugacity coefcient, it is dimensionless and can V~ c;i  V~ c;j
be calculated through an EoS. The PengRobinson EoS was chosen, ki;j 1  8 q q 15
V c;j 3
3 ~ 3 ~
which has been extensively used (Tang and Kitagawa, 2005; Voll V c;i
et al., 2009) on account of its capability of dealing effectively with
supercritical uids. Matrix E is assumed to be null, thus neglecting the effect of gij,
PengRobinson EoS describes the link between system pres- as suggested by McHugh and Krukonis (1994).
sure, temperature and molar volume by resorting to parameters Once Z for the whole mixture is calculated, the resulting value
derived from critical properties of the substances, such as critical can be used to determine the fugacity coefcient ui of the i-th
temperature Tc, critical pressure Pc and acentric factor x. For a pure component of the mixture:
substance, it has the following form: 
bi
lnui Z  1  lnZ  B
RT a bm
P  6 0 N 1
V~  b V~ 2 2bV~  b2 P
B 2 xj ai;j C
Parameters a and b depend on the critical properties and are de- A B j1 b C Z 2:414B
 B  i C ln 16
ned as follows: 2:828B @ am bm A Z  0:414B
" s!#2
0:45724R2 T 2c T
a 1 0:37464 1:54226x  0:26992x2 1 
Pc Tc where
7
am
A P 17
0:07780 RT c R2 T 2
b 8
Pc
bm
Eq. (6) can also be expressed in a different way by introducing B P 18
RT
the dimensionless compressibility factor Z:
X
N
PV~ 
bi 2 xj bij  bm 19
Z 9
RT j1
D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582 7577

Table 1
Chemical species considered in the model, along with their critical parameters (NIST-TRC databank).

Tc [K] Pc [Pa] ~ c [m3/kmol]


V x []
Oxygen O2 154.644 5042190 0.07351871 0.0213195
Hydrogen H2 33.172 1239720 0.06473499 0.232001
Water H2O 647.296 22140200 0.05629781 0.343897
Solid carbon C 6810 223000000 0.0188 0.326841
Methane CH4 190.562 4607790 0.09925631 0.0106362
Carbon monoxide CO 134.464 3774230 0.09062499 0.0370708
Carbon dioxide CO2 304.169 7378280 0.0942549 0.224877
Nitrous oxide N2O 309.565 7241650 0.09778602 0.1611
Ammonia NH3 405.6 11277473 0.072362166 0.25
Nitric oxide NO 180 6484800 0.057693375 0.607
Nitrogen dioxide NO2 431.4 10132500 0.16990837 0.86
Nitrogen N2 128.464 3094240 0.08616066 0.04
Propane C3H8 369.859 4255660 0.1986718 0.152919
Ethane C2H6 305.367 4885500 0.1461753 0.100161
Ethylene C2H4 282.345 5042360 0.1310267 0.0864047
Methanol CH3OH 512.658 8012950 0.1165915 0.55967
Acetylene C2H2 308.341 6239770 0.1190043 0.185731
Methyl-acetylene C3H4 401.564 5625550 0.1614438 0.209058
Propylene C3H6 364.933 4594260 0.1830666 0.14218
Benzene C6H6 561.99 4897390 0.2566344 0.21047
Naphthalene C10H8 748.191 4081640 0.4075999 0.307871
Formaldehyde CH2O 418 6853840 0.1043348 0.201805

The model accounts for the presence of a solid phase, repre- expansion, glycerol world production has increased from
sented by graphitic carbon and indicating char formation. In order 500,000 tons in 1991 to currently 2,500,000 tons a year. Today,
to calculate the chemical potential for the solid phase, Eq. (2) must the biodiesel industry accounts for 70% of worldwide glycerol pro-
be revised, since it has been derived for a gas. From the denition duction (Henard, 2007). This enormous quantity of glycerol is dif-
of Gibbs free energy: cultly absorbed through traditional channels (e.g. cosmetics, pet
Z P
food). Therefore, glycerol has become an industrial waste. SCWG
lT; P l0 T ~
VdP 20 could be an effective way to dispose of this substance and, at the
P0 same time, convert it into a valuable gas with a high H2 content.
~ can be reasonably considered to Finally, experimental data about glycerol SCWG are available in
For a solid, the molar volume V
the literature, thus a model validation can be performed for this
be constant, thus it can be taken outside the sign of integration.
~c compound.
Moreover, since the volume is constant, the critical volume V
In addition, some analyses were conducted on microalga Spiru-
can be used. The integration is, then, immediate:
lina, a blue-green alga which is very common as a dietary supple-
lT; P l0 T V~ c P  P0 21 ment for both humans and animals. Algae are biomass with a great
potential for exploitation, since they can be easily grown by only
using water, CO2 and solar energy. They can also be cultivated
3. Model implementation and validation resorting to municipal or agro-industrial wastewater. Moreover,
since algae normally possess a high water content, they seem par-
The model was implemented by using the MatLab software ticularly suitable for hydrothermal treatment, while traditional
(The Mathworks Inc.). In order to perform the minimization of gasication technologies, which require dry biomass, seem less
Gibbs free energy, the routine FMINCON was used. This routine applicable to them (Jena et al., 2011).
is based on the method of Lagrange multipliers, which enables to Microalga Spirulina was modeled as a pseudo-compound whose
solve a minimization problem subject to constraints. formula is CxHyOzNw. Coefcients x, y, z and w were computed
In this case, the problem consists in nding a composition for according to the dry ash-free ultimate analysis, which was pro-
the system which corresponds to the minimum value for G. This vided by the database Phyllis (ECN), where x was considered
problem is subject to two constraints: (a) mass conservation, inso- equal to 1. As a result, microalga Spirulina was modeled as a com-
far as the amount of each element (C, H, O, N) must be the same in pound whose molecular formula is C1H1.8655O0.5893N0.1275.
the input (reagents) and output (products) streams; (b) non-nega- Among the output compounds, 22 different species were se-
tivity of the number of moles ni. The latter is very important, since lected as representative of the main categories of compounds
to obtain a solution which can respect the mass balance is numer- which can be reasonably found in the output stream. Besides the
ically possible but completely meaningless owing to the negative standard products like H2O, H2, CO, CO2, and CH4, C24 hydrocar-
number of moles. bons and PAH were considered, as well as N2, NH3 and nitrogen
The input stream composition is only useful in order to dene oxides. The complete list of output compounds, along with their
the mass balances and to calculate its enthalpy. All the simulations critical parameters, is reported in Table 1.
foresee an input stream composed of water, biomass and, possibly, The model results were compared with the experimental data
pure oxygen (O2) as oxidizing agent. by Byrd et al. (2008), who carried out a study on the SCWG of
Most analyses are conducted with glycerol (C3H8O3). Glycerol glycerol with a Ru/Al2O3 catalyst. The results of model testing
can be considered a model compound for common biomass, since are shown in Fig. 1, where the syngas composition is reported
its molecule reproduces typical ratios of carbon, hydrogen and oxy- as a function of the feed concentration expressed in weight
gen, which are the most important constituents of biomass. Glyc- basis. To mention an example, a feed concentration of 20%
erol also plays a major role as the most abundant co-product in corresponds to a feed consisting of water (80%) and dry glycerol
biodiesel production plants. As a result of the biodiesel industry (20%).
7578 D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582

Fig. 1. Model validation with experimental data from Byrd et al. (2008).

In order to compare model predictions and experimental results the products preferred, besides water, are hydrogen and carbon
quantitatively, Pearsons correlation coefcient r was used, where a dioxide. Up to a feed concentration of 10%, H2, CO2 and H2O are al-
value of 0 stands for no correlation and a value of 1 means optimal most the only products at equilibrium. When the feed concentra-
correlation. tion increases, CH4 and CO form at equilibrium. Hydrogen
As far as hydrogen is concerned, the agreement between exper- production reaches its maximum at a feed concentration of about
imental data and model predictions is found to be very good 40% and subsequently starts to decrease, while methane produc-
(r = 0.988), which demonstrates that the model is able to predict tion increases. All trends are quite regular up to a feed concentra-
hydrogen yields in a very effective way. tion of 72%, the minimum concentration at which solid carbon is
The situation is slightly different for other gaseous species expected at equilibrium. At this point a noticeable change in the
(methane, carbon monoxide, and carbon dioxide). In this case, slope of all curves involving gaseous carbon compounds occurs,
the agreement between model and experimental results is accept- and their molar fraction starts to decrease.
able, the model output and the experimental data follow approxi- The situation is completely different when working at a lower
mately the same trend, but the tting is not perfect. The correlation temperature. Fig. 2b shows the equilibrium behavior resulting
coefcient is still high for methane (r = 0.984), lower but tolerable from the SCWG of the same compound at the same pressure, but
for carbon dioxide (r = 0.728), very low for carbon monoxide with a temperature of 500 C. Signicantly, hydrogen production
(r = 0.469). is far lower than in the previous case, while methane is also found
In general, it is possible to state that the model implemented at low feed concentrations. Carbon monoxide is almost absent at
provides results which are in good accordance with experimental equilibrium. In this case an evident change in the slope can also
data and, therefore, the model is a valuable tool for predicting be observed by the time solid carbon forms at equilibrium. How-
the thermodynamics constraints of the SCWG process. ever, at lower temperatures, solid carbon forms at lower feed con-
centrations: at 500 C it forms with a feed concentration of 60%.
Fig. 2c shows the equilibrium composition as a function of tem-
4. Results and discussion
perature for the SCWG of glycerol at 250 bar and feed concentra-
tion of 80%. Water was not included in the diagram for the sake
Two different types of analysis were performed through the
of readability. An increase in temperature plays a favorable role
model proposed. The rst class is aimed at describing the two-
for hydrogen and carbon monoxide formation, while methane
phase behavior of the reacting system, i.e. the process conditions
and carbon dioxide are preferred at mediumlow temperatures.
that cause the output stream containing solid carbon. The second
Similar trends were observed in the case of atmospheric pressure
approach is focused on energy aspects, with a view to investigating
steam gasication of pine sawdust (Gao et al., 2009). The formation
the reaction energy requirements and the amount of energy con-
of solid carbon is thwarted at high temperature. Indeed char is
tained in the product gas.
found up to 900 C.
High pressure is favorable for char formation, as shown in
4.1. Char formation Fig. 2d. Below 10 bar no char is expected at 800 C for an 80% wt.
feeding stream. The effect of pressure is that of minimizing the
The model was rst run to state the dependence of the compo- overall volume of the system. Therefore, a solid, whose specic vol-
sition of the reaction products (syngas and possibly solid carbon) ume is normally far lower than that of a gas, is denitely
as a function of the biomass concentration in the feed. advantaged.
Fig. 2a shows the composition of the syngas produced through The same analyses were conducted on microalga Spirulina: see
the SCWG of glycerol at 800 C and 250 bar. Water was excluded Fig. 3. All analyses point to trends which are very similar to those
from the plot in order to improve its readability. Clearly, the syngas observed in studies on glycerol (Fig. 2). On the other hand, it is evi-
composition signicantly varies with the feed concentration (ex- dent that the conditions leading to formation of a solid phase for
pressed in weight basis as for Fig. 1). At low feed concentrations, microalgae are substantially different than for glycerol. Solid
D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582 7579

Fig. 2. Model results for the SCWG of glycerol under different operating conditions. (a) Equilibrium composition versus feed concentration (T = 800 C, P = 250 bar); (b)
equilibrium composition versus feed concentration (T = 500 C, P = 250 bar); (c) equilibrium composition versus temperature (P = 250 bar, feed concentration = 80%); (d)
equilibrium composition versus pressure (T = 800 C, feed concentration = 80%).

Fig. 3. Model results for the SCWG of microalga Spirulina under different operating conditions. (a) Equilibrium composition versus feed concentration (T = 800 C,
P = 250 bar); (b) equilibrium composition versus feed concentration (T = 500 C, P = 250 bar); (c) equilibrium composition versus temperature (P = 250 bar, feed
concentration = 60%); (d) equilibrium composition versus pressure (T = 800 C, feed concentration = 60%).

carbon forms at lower feed concentrations and pressure and at situation where only the supercritical phase is found at equilib-
higher temperatures. The formation of a solid phase seems to be rium to one where solid carbon is also found at equilibrium. In
easier for this type of biomass, i.e. for a substance with this spe- the case of microalga Spirulina, with a feed concentration of 80%
cic ratios of carbon, hydrogen and oxygen. (value utilized for the SCWG of glycerol, see Fig. 2c and d) solid car-
While Fig. 3a and b can be directly compared with Fig. 2a and b bon is found at equilibrium at 250 bar in the whole range of tem-
(temperatures and pressures coincide), this does not apply to other perature analyzed.
gures. Fig. 3c and d were, indeed, obtained with a feed concentra- The analysis with microalga Spirulina also enables to account for
tion of 60% (with 40% of the feed consisting of water and 60% of dry the presence of nitrogen compounds. Looking at Fig. 3ad, nitrogen
biomass C1H1.8655O0.5893N0.1275). This highlights the shift from a is only found as N2 in the product gas. Its molar fractions in the
7580 D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582

syngas seem to be solely determined by the biomass concentration favored, as also demonstrated by Figs. 2d and 3d. Fig. 4b reveals
in the feed. Neither temperature nor pressure appear to inuence that the char formation region signicantly enlarges when
N2 concentrations signicantly. increasing pressure from 1 to 100 bar. However, in the typical pres-
A parameter signicantly inuencing the formation of char in sure range of hydrothermal treatments, the effect of pressure on
the SCWG process is the elemental composition of the biomass char formation is very limited: looking at Fig. 4b, the curves corre-
used, as demonstrated by comparing the model results for glycerol sponding to 100 and 500 bar almost overlap.
with the ones for microalga Spirulina. Interestingly, these ternary plots can also be used for a generic
In order to account for different types of biomass, a representa- biomass feed with an arbitrary water/biomass ratio. It is just nec-
tion based on ternary diagrams was adopted. In this depiction, essary to consider the amount of water in the calculation of the
each of the three axes of the diagram stands for the molar fraction stoichiometric index x, y and z. The new point in the plot will then
of C, H and O in the biomass pseudo-molecule, represented by the represent the SCWG of the considered biomass at the concentra-
simplied formula CxHyOz (nitrogen was neglected for this pur- tion desired. This is possible because the equilibrium composition
pose). With this schematization, each biomass is represented by of the system is determined by the relative amount of C, H and O
a point in the ternary diagram. supplied with the reagent stream, regardless of its actual
Each axis of the ternary plot was divided into 50 intervals. For composition.
each point inside the triangle, a different run of the model was then
performed to verify whether, for that particular biomass composi- 4.2. Energy analysis
tion, graphitic carbon had been expected or not at equilibrium.
Thus, these simulations are representative of a biomass concentra- Another series of simulations were performed to evaluate the
tion of 100%, which is the most favorable condition for char energy needs of the SCWG process. The process heat duty was cal-
formation. culated under different process conditions, i.e. by varying biomass
Fig. 4a shows the results of the analysis when the system tem- concentration and temperature.
perature was changed, holding the pressure constant at 250 bar. It In order to calculate the process heat duty, isothermal opera-
is possible to see that, in general, biomass with a high oxygen con- tions were considered. Therefore, reagents and products are at
tent (upper zone of the diagram) does not cause the formation of the same temperature and the heat produced or required for the
solid carbon. This is also true for low carbon content feedstock. reaction (DH) is calculated as the difference between the enthalpy
The region where solid carbon is found is that in the bottom-left of the products and that of the reagents. In order to gain informa-
part of the triangle. However, the boundaries of this region are tion on the quality of the product gas, its high heating value (HHV)
inuenced by temperature. High temperature discourages carbon was calculated, neglecting its water content.
formation, as more energy is available for carbon to perform Importantly, this approach only considers the amount of ther-
reforming reactions. Fig. 4a reects this statement, inasmuch as mal energy required for (or provided by) the reaction itself. The en-
the char formation region is slightly wider at 400 C than at ergy required for the whole process is normally higher, because the
800 C and 1200 C. On the other hand, there is a small region input stream has to be heated up to the reaction temperature and it
around H = 0.8 and O between 0 and 0.1 where the three curves in- is not possible to recover all the sensible heat of the product
vert their order, thus allowing for a char production favored by an stream to warm up the reagent stream.
increase in temperature. Moreover, the possibility of using an oxidizing agent like O2 was
Fig. 4b shows the results of the same analysis conducted under taken into account, in order to simulate the effect of a partial oxi-
different pressure conditions, while temperature was kept at dation of the biomass. The amount of oxidizing agent was ex-
800 C. Pressure plays an important role in char formation, as char pressed in terms of equivalence ratio (ER), i.e. the ratio between
formation is facilitated by high pressure. This can be easily ex- the quantity of O2 which is used and the amount of O2 required
plained from a thermodynamic perspective, since high pressure for the complete stoichiometric oxidization of the considered bio-
favors reactions determining a decrease in the total volume of mass. Starting from the stoichiometric reaction for biomass com-
the system. Under high pressure conditions solids are therefore bustion, ER was dened as:

Fig. 4. Ternary diagram for a generic biomass schematized by the pseudo-molecule CxHyOz. Values on the axes refer to the molar ratios of C, H and O in the biomass molecule.
(a) Char formation at varying temperature (P = 250 bar); (b) char formation at varying pressure (T = 800 C).
D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582 7581

Fig. 5. Energy analysis for the SCWG of glycerol as a function of temperature and equivalence ratio ER () (P = 250 bar, feed concentration = 10%). (a) Reaction heat duty; (b)
HHV of the product gas on dry basis.

Fig. 6. Energy analysis for the SCWG of glycerol as a function of temperature and feed concentration (P = 250 bar, ER = 0). (a) Reaction heat duty; (b) HHV of the product gas
on dry basis; (c) product gas yields per unit mass of fed glycerol; (d) energy yields for the complete oxidation of the product gas derived by a unit mass of fed glycerol.

nO2 Similar considerations apply also to the energy analysis con-


ER   22
x 4y  2z nbio ducted for the SCWG of microalga Spirulina (the model results
Fig. 5 shows the heat duty and the HHV of the product gas for are not reported for sake of brevity).
SCWG of glycerol at a concentration of 10% on weight basis, at A similar analysis was performed where ER was kept null and
varying temperatures and equivalence ratios (ERs). If no oxidizing glycerol concentration in the feed was increased from 5% to
agent is used, SCWG is weakly exothermic for temperatures below 100%. Results are presented in Fig. 6. Fig. 6a shows that, as temper-
680 C and weakly endothermic above 680 C. If oxygen is added to ature increases, the reaction requires more energy. Operations are
the reagent stream, exothermic operations result in the whole exothermic at lower temperature and then become endothermic as
range of temperatures analyzed, even with slight amounts of O2. temperature rises. It is possible to observe a temperature at which
As ER increases, the HHV of the product gas decreases. At ER = 1, the reaction is energetically neutral: above it, operations are endo-
the product gas shows a null heating value, since all combustible thermic, while below it they are exothermic. For a feedstock con-
gases are oxidized. centration of 5%, this temperature is of approximately 580 C; for
7582 D. Castello, L. Fiori / Bioresource Technology 102 (2011) 75747582

a 100% glycerol feed, this temperature is 1050 C. This suggests Isothermal energy analysis applied to glycerol shows that
that the energy demand of the reaction decreases as the feed con- SCWG is weakly exothermic for temperatures below 680 C and
centration increases. On the other hand, it is possible to observe weakly endothermic above 680 C. But if a small amount of O2 is
that, at high temperature, a higher glycerol concentration leads added (ER = 0.2), SCWG becomes exothermic in the whole temper-
to slightly higher energy needs for the process (see the upper-right ature range analyzed (4001200 C).
portion of Fig. 6a where the curves cross). In any case, the amount
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