Chemical Engineering Journal 286 (2016) 663–678

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

A modelling approach to the techno-economics of Biomass-to-SNG/

Methanol systems: Standalone vs Integrated topologies
Luis E. Arteaga-Pérez a,⇑, Oscar Gómez-Cápiro b, Alejandro Karelovic b, Romel Jiménez b,⇑
a
Technological Development Unit, University of Concepción, Chile
b
Department of Chemical Engineering, University of Concepción, Chile

h i g h l i g h t s

A model on biomass gasification integrated to Methanol and SNG production.

CAPEX/OPEX evaluation for standalone and integrated process topologies.

Sensitivity of energy costs to the operation and market variables.

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

Article history: Chile accounts for one of the most important forest areas in Latin America; nevertheless, both Chilean
Received 15 June 2015 energy and chemical infrastructures heavily relies on imported fossil fuels. This study focuses on the
Received in revised form 26 October 2015 analysis of several scenarios contributing to change this status quo by producing biomass-based
Accepted 2 November 2015
Methanol and Synthetic Natural Gas (SNG). A comprehensive flowsheeting model, including such tech-
Available online 11 November 2015
nologies, is developed and validated. The plants are assembled in a general superstructure to perform
their energy integration and economic evaluation. For the studied scenarios, the energy efficiency of gasi-
Keywords:
fier was 74%; Methanol and SNG yields were 0.59 kgMeOH/kgDry-biomass and 0.33 kgSNG/kgDry-biomass, respec-
Biomass
Gasification
tively. The biomass-derived SNG has an average of 88% mol of methane and a Lower Heating Value of
Synthetic Natural Gas 41 MJ/kg. The unit energy cost ($/GJ) via SNG and Methanol were 18.41 $/GJ and 29.54 $/GJ for stan-
Methanol dalone operation, and both can be reduced by 12.7% and 9.5%, respectively, by using an integrated process
scheme. Finally, near 25% of sensitivity on unit cost of products (energy based) was found when the feed-
stock price varied between 1 and 60 US$/tonne.
Ó 2015 Elsevier B.V. All rights reserved.

1. Introduction poor exploitation of distribution facilities. The effect of this

In the view of the shortage of fossil fuels and their derivatives,
switching from unsecure and polluting petro-based economy to
bio-economy has been envisaged as the conscious way to reach
sustainable development standards. This statement becomes more
important for developing countries like Chile, which has experi-
enced a fast economic growth in the last decades, with a propor-
tional effect on the energy demand (1.42 EJ in 2013) [1].
Furthermore, the consumption of primary energy in Chile heavily
relies on imported fossil fuels, mainly oil (30%), coal (22%) and nat-
ural gas (13%) [1]. Specifically, the natural gas supply was reduced
from 266.25 PJ/y in 2004 to only 151.64 PJ/y in 2013, leading to a
⇑ Corresponding authors. Tel.: +56 (41) 266 1855; fax: +56 (41) 275 1233 (L.E.
Arteaga-Pérez). Tel.: +56 (41) 266 4762 (R. Jiménez).
E-mail addresses: l.arteaga@udt.cl (L.E. Arteaga-Pérez), romeljimenez@udec.cl
(R. Jiménez).
suppression was also critical for the national Methanol market,
which reduced its production capacity to a minimum of 7.6% in ref-
erence to 2004 (61.01 PJ/y). Due to this situation, the government
has established policies for the development of new and more sus-
tainable technologies [2]. In this framework, forest biomass
appears as a prospective candidate, based on its abundance,
renewability, carbon neutrality, and the possibility of conversion
to higher-value-added products. Chile accounts for more than
15 million hectares of native and forest plantations, the latter with
an average yield of 35 m3/ha/y [3]. Main species in Chilean wood
plantations are Pinus radiata (60.9%), Eucalyptus globulus (22.4%)
and Eucalyptus nitens (9.6%) [2]. These special features give the
country an enormous potential to develop biomass-to-fuels and
biomass-to-chemicals technologies [4,5], among which Synthetic
Natural Gas (SNG) and Methanol are of special interest.
The advantages of converting biomass into SNG are the high
yield (0.20–0.40 kgSNG/kgDry,biomass), the possibility of long-term

http://dx.doi.org/10.1016/j.cej.2015.11.005
1385-8947/Ó 2015 Elsevier B.V. All rights reserved.
664 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678

Nomenclature

A area (m2) GHG Green House Gases

Cin carbon flow of inlet biomass (kmol/h) G-Integrated Gasification integrated to Methanol and SNG
Cu unconverted carbon (kmol/h) G-MSL Gasification integrated to Methanol
Dp particle diameter (lm) G-SNG Gasification integrated to SNG
ER equivalence ratio = actual flow of oxidant/oxidant HEN heat exchanger network
required for complete combustion HPS High pressure steam
F CH4 mole flow of CH4 in gasification gases (kmol/h) LPS Low pressure steam
FCO mole flow of CO in gasification gases (kmol/h) MeOH Methanol
F CO2 mole flow of CO2 in gasification gases (kmol/h) MI Marshal and Swift cost index
FMeOH mass flow of Methanol (kg/h) MPS Medium pressure steam
LHV Lower Heating Value (MJ/kg) MSL Methanol synthesis loop
P pressure (atm) MSW municipal solid wastes
Q heat consumption (kW) OPEX Operational Expenses
T temperature (°C) PFD Process Flow Diagram
XCO-1R conversion of CO in the 1st methanator PSA pressure swing adsorption
Xe equilibrium conversion (%) R/P recycle to purge ratio
Xr real conversion (%) SN stoichiometric number
yexperimental,i measured mole fraction of component (i) in gasifica- SNG Synthetic Natural Gas
tion gas TCI total capital investment
YMeOH mass yield of Methanol (kgMeOH/kgDry-biomass) WGSR Water gas shift reaction
ymodel,i calculated mole fraction of component (i) in gasification
gas Greek letters
gBtoF efficiency in biomass to fuel conversion (%)
Acronyms gth global thermal efficiency (%)
CAPEX Capital Expenses
GCC Grand Composite Curve

exploitation of already existing gas distribution infrastructure and
the well-established and efficient end use technologies (e.g. com-
bined heat and power, power stations, domestic heating) [6,7]. Bio-
mass can be converted to SNG by using different processes [7,8]; as
detailed in Kopysinsky et al. [7]. First stage is biomass gasification
to produce a syngas followed by a cleaning section, which involve
physical and chemical treatments to eliminate tars, alkali and par-
ticulate [5]. After that, the CO/H2 ratio of the syngas is adjusted in a
WGSR reactor. Thereafter, the gas is fed to the methanation system
(SNG synthesis) where carbon oxides and hydrogen are converted
into CH4 and H2O. Subsequently, unconverted CO2 and moisture
are removed from the ‘‘crude” SNG prior to its injection into the
distribution grid (see Fig. 1). The overall efficiency of the process
is function of the individual contributions of gasification, cleaning
and methanation, hence the level of integration and energy man-
agement among systems is critical to achieve the desired results
[7]. Up to date, there are several works on the design and evalua-
tion of Biomass to SNG technologies, all of them based on different
modeling approaches and for different biomass sources. Van der
Meijden [8] analyzed, the overall energy efficiency and the CO2
emissions of three wood gasification systems integrated to the
SNG production, and suggested that CO2 balance can be neutral
and even negative if CO2 is stored. Net efficiency (excluding trans-
port) for the three systems varied between 54% and 67%. Neverthe-
less, no details on the modeling approach were provided and the
analysis did not include a heat integration study. Similarly,
Vitasarai et al. [6], performed the exergy evaluation of SNG produc-
tion using three different feedstock (e.g. virgin woody, municipal
solid wastes (MSW) and sludge). In this study, maximum exergy
destruction and irreversibilities were identified in the gasifier
and methanation reactors, while higher exergy efficiencies
were found for woody biomass (53–58%) as compared to the
other feedstock. The highest SNG yields were estimated for
woody biomass (0.28–0.31 kgSNG/kgDry,feedstock) and sludge
(0.20–0.23 kgSNG/kgDry,feedstock), respectively. No heat integration
was carried out and the effect of using an equilibrium model for
gasification on the global exergetic efficiency was neglected. In
an earlier work, Mozaffarian and Zwart [9] studied the technical,
economic and environmental prospectives of waste/biomass to
SNG process. The calculated unit cost of SNG was sensible to the
production capacity, being lower (8.7 $/GJ) for a plant of 15 PJ/y.
The thermoeconomic performance of different scenarios for SNG
production from lignocellulosic biomass was analyzed by Gassner
and Maréchal [10]. They concluded that higher energy and exergy
efficiencies (69–76% and 63–69%, respectively) can be obtained for
integrated plants [6,8]. The production cost of SNG (integrated
plant), including the depreciation, varied between 21 €/GJ and
29.7 €/GJ for a plant capacity of 20 MWth,biomass whereas these
values can be further reduced to 16.38 €/GJ for a higher plant
capacity (150 MWth,biomass).
Biomass-based Methanol is also a good alternative to replace
fossil fuels (e.g. gasoline in conventional spark engines), requiring
only moderate changes in the fuel distribution infrastructure
[11]. Such opportunity was envisaged by Andersson et al. [11],
which have recently investigated the techno-economic feasibility
of integrating gasification-based biomass-to-Methanol production
in an industrial facility (pulp and paper mill). They suggested the
need of a special policy support to make bio-Methanol production
competitive; in such a case, the price can be reduced to 3.05–5
€/GJ. Moreover, authors found that using integration, the energy
efficiency of the original process could increment by 7%. Similarly,
Brachi et al. [12] studied the co-gasification of biomass and poly-
meric wastes for Methanol production. The analyses were
performed in a pilot-scale fluidized bed gasifier using air and steam
as oxidizing media. The best results regarding syngas composition,
relevant to Methanol production, were achieved for biomass,
keeping the gasifier temperature above 750 °C and low equiva-
lence ratios (ER) (<0.1). A more complete analysis of Methanol
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678 665

Fig. 1. Flowsheet of biomass gasification integrated to Methanol (MSL) and SNG production. Q and Q+ represent the heat evolved in exothermic and endothermic processes,
respectively.

production from biomass was reported by Holmgreen et al. [13,14] market. These hypotheses are scrutinized here, through the appli-
and Clausen et al. [15]. The former demonstrated that integrated cation of process synthesis techniques to both Standalone and Inte-
systems have greater potential to reduce Green House Gas (GHG) grated Methanol/SNG topologies.
emissions than the standalone systems. Moreover, they also found
that the biomass drying had significant impact on the overall energy 2. Plant configurations. Biomass-to-SNG/Methanol
balance (Cooling utilities increased by 60%). Furthermore, replacing
WGSR by direct hydrogen addition can increase the Methanol yield, The possibilities of integration for Biomass Gasification-to-SNG/
by 35%. On the other hand, Clausen et al. [15] compared six plant con- Methanol processes are assessed. A simplified block diagram of the
figurations, each with a different biomass-to-syngas production studied systems is presented in Fig. 1. Further expansion of process
method. Exergy efficiencies for Methanol production varied diagrams within each block is provided in Section 4.
between 59% and 72%, the best for a configuration incorporating Syngas is produced from biomass gasification and afterwards
autothermal reforming of biogas and electrolysis of water. The speci- through cleaning and conditioning stages prior the two synthesis
fic Methanol costs for the six plants were in the range 11.8–25.3 loops (SNG and Methanol). Systems integration is performed
€/GJexergy. Among the revised literature there are several papers through PINCH analysis, a methodology dealing in the first place,
(Table 1) on the design and simulation of both Biomass-to- with the optimal management of energy as well as with the design
Methanol and Biomass-to-SNG systems. Nevertheless, only few of of the corresponding heat exchanger network. For a detailed
these works focused on the integration and techno-economic assess- description of PINCH methodology please see Dimian [19] and
ment of systems. Among the revised literature, there are several Seader et al. [20].
papers (Table 1) on the design and simulation of both Biomass-
to-Methanol and Biomass-to-SNG systems. Nevertheless, very few 3. Feedstock characterization
of those works focused on the integration and techno-economic val-
uation of such systems considering a common superstructure. Fur- The case studies presented here correspond to conditions found
thermore, it is worth noticing that the estimations summarized in in Chile, where most of forest plantations (>60%) are P. radiata [21].
Table 1 are only referential, because they can significantly differ This specie is not only crucial for the forest industry but also for the
depending on processes topologies and feedstock nature. future development of the Chilean energy matrix [22]. Samples
Therefore, the feasibility of producing SNG and Methanol from were characterized by the standard practice for proximate analysis
forest biomass in Chile is assessed. According to the prior discus- of coal and coke (D3172-89) and elemental analysis according to
sion, the production of both SNG and Methanol, may be highly ABNT-NBR-8112 (‘‘Determination of ash, volatile matter and fixed
influenced by the process topology and the behavior of biomass carbon in vegetal charcoal”) in a Leco True Spec elemental analyzer
(Thermo Finningan. model Flash EA series 1112). Results are sum-
marized in Table 2 along with other feedstock that have been used
Table 1
Performance indicators of biomass to Methanol and SNG systems. in gasification. Data regarding process conditions, efficiencies as
well as producer gas compositions for these materials are available
Plant gth (%) Biofuel yield gB–F (%) Ref.
in the cited references, therefore, they will be considered for model
(kgfuel/kgBiomass)
validation.
Gasification to SNG – 0.24–0.26 53–58 [6] Among values shown in Table 2, moisture (MC), ash and carbon
Gasification to SNG 58.10 0.23–0.25 52–55 [8]
Gasification to SNG 69 0.302–0.33 67–72 [10]
(%C) contents are the most important parameters for thermal con-
Gasification to Methanol 46.2 0.32–0.28 35–31 [11] version processes (gasification and/or combustion) as they define
Gasification to Methanol–SNG 59–72 0.68–0.81 81–90 [14] the gases composition and its final applications [29]. The high car-
Gasification to Methanol 42–45 0.258–0.31 29–34 [16] bon content and absence of sulfur of P. radiata makes it a potential
Gasification to Methanol 54 0.256 28.40 [17]
feedstock for gasification to chemicals and/or energy applications
Gasification to SNG 67 0.303 67.40 [18]
[27]. The calculated O/C and H/C molar ratios for biomass, places
666 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678

Table 2
Proximate and ultimate analyses of biomass from different sources. Dry weight basis.

Material Ultimate analysis Proximate

* *
%C %H %O %N %S MC VM** FC** Ash O/C H/C Ref.
Pinus radiata sawdust 48.94 6.91 43.73 0.12 <0.01 6.82 77.71 15.17 0.30 0.67 1.69 This work
Bamboo 48.38 5.86 39.21 2.09 0.0 10.0 72.00 13.54 4.46 0.61 1.45 [23]
Gulmohar 44.43 6.16 41.90 1.65 0.0 10.0 73.13 11.92 5.86 0.71 1.66 [23]
Neem 45.10 6.00 41.50 1.70 0.0 10.0 73.00 11.30 5.70 0.69 1.60 [23]
MSW1 30.77 4.62 17.30 0.77 0.0 48.0 24.00 4.00 24.00 0.42 1.80 [24]
MSW2 36.35 4.96 10.13 1.43 0.83 50.90 18.80 7.60 22.70 0.21 1.64 [25]
Wood pellet 51.02 7.16 41.73 0.09 0.004 9.80 72.70 16.70 0.80 0.61 1.68 [26]
Pine sawdust 50.54 7.08 41.11 0.15 0.57 10.0 82.29 17.16 0.55 0.61 1.68 [27]
Eucalyptus 46.78 5.92 45.55 0.324 0.09 12.23 83.01 15.66 1.84 0.73 1.52 [28]
*
Oxygen is calculated by difference.
**
MC: moisture content, VM: volatile matter, FC: fixed carbon.

all them into the same classification zone (between biomass and
lignin) according to the van Krevelen diagram [30]; except for
municipal solid wastes (MSW) which are in the region of immature
oil or diagenesis.
4. Systems modeling
A plant model for biomass gasification integrated to the produc-
tion of Methanol and SNG (Fig. 1) is developed using Aspen One
v8.6 software. The gasification system is modeled considering a
quasi-equilibrium approach and it is calibrated against experimen-
tal data. Methanol plant is modeled based on the REtrol vision and
on the results reported by Clausen et al. [15]; while the SNG sys-
tem uses the ICI/Koppers process concepts presented by Vitasari
et al. [6] and Kopysinsky et al. [7].
4.1. Gasification section. Model description
There is a growing interest in the modeling of gasification sys-
tems to assess its integration with energy and chemicals produc-
tion into the so-called biorefinery concept. In that sense, there
are reports on (i) kinetic [29], (ii) stoichiometric, (iii) non-
stoichiometric and (iv) Quasi-equilibrium-based models
[23,25,29,31–33]. In spite of their popularity, the purely thermody-
namic equilibrium models are limited for describing real processes,
since they neglects deviations due to kinetic, mass and heat trans-
fer resistances. The quasi-equilibrium approach allows quantifying
deviations from thermodynamic equilibrium providing a more
realistic gas composition [33,34]. When compared to kinetic mod-
els, this approach has the advantage of being more general,
because it is not associated to the resistances affecting the kinetics
of gasification [29]. Therefore, a quasi-equilibrium model has been
adopted here to study the biomass-to-syngas conversion process. A
scheme of the model is presented in Fig. 2.
For modeling purposes, the gasification process is divided into
several sub-units to simulate drying, pyrolysis, gasification and
producer gas cleaning systems. As it has been reported elsewhere
[35–37], gasification is a complex process involving decomposition
and oxidation reactions in solid and gas phases. The process takes
place when air, oxygen, steam or water react with carbon from
feedstock structure to produce a gas stream (producer gas) con-
taining: H2, CO, CH4, CxHy, CO2 and impurities such as tars, ammo-
nia, sulfur, chlorine compounds and alkalis. Although this
composition can substantially change, depending on the gasifica-
tion media, reactor design and feedstock nature, most of systems
require cleaning stages prior to downstream applications [5].
Accordingly, the following approximations were considered: (i)
steady state calculations, (ii) biomass is defined as non-
conventional solid using proximate and ultimate analysis, (iii) char
is represented as a conventional solid (graphite) with specific ther-
modynamic properties, (iv) thermodynamic properties in gasifica-
tion are estimated using the Redlich–Kwong–Soave (RKS) equation
of state, (v) air is represented as 79% N2 and 21% O2 molar basis.
4.1.1. Operations models
Biomass dryer: Two Aspen blocks were used to simulate drying:
a stoichiometric reactor (GS-01) and a flash separator (GS-02). The
wet feedstock (pine) enters at atmospheric conditions (298 K and

Fig. 2. PFD of gasification plant model.

 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
101.325 kPa) and with 30–50% moisture content (mass wet basis).
The moisture content is then reduced to 10%. Although drying is
not usually considered a chemical reaction, this approximation
allows converting a fraction of nonconventional component (mois-
ture) to conventional water in Aspen One, and to calculate the heat
needed to vaporize this water. A FORTRAN block is used to solve
the mass balance in the process.
Gasifier: The gasification reactor is divided into several unit
operation blocks (GS-03, GS-05, GS-06 and GS-07) to introduce
the approximations of the model. The Gibbs free energy of biomass
cannot be estimated, because it is a nonconventional component.
Therefore, block GS-03 (yield reactor) is used to convert the non-
conventional composition (ultimate analysis) into its analogues
(C, H, O, N and S), prior solving the gasifier module. This block is
solved by a FORTRAN subroutine, which specifies the yields on
wet basis.
Gasification (GS-05 and GS-06) module was solved to estimate
the composition of the producer gas by integrating two modeling
approaches [23,29]:
First: A purely equilibrium model, solved through the Minimiza-
tion of the Gibbs free energy method for all the possible com-
pounds in the following reaction scheme:
Heterogeneous reactions:
C þ 1=2O2 $ CO DH ¼ 111 kJ=mol
C þ CO2 $ 2CO DH ¼ þ172 kJ=mol ðBoudouardÞ
C þ H2 O $ CO þ H2 DH ¼ þ131 kJ=mol
C þ 2H2 $ CH4 DH ¼ 75 kJ=mol
Homogeneous reactions:
CO þ H2 O $ H2 þ CO2 DH ¼ 41 kJ=mol ðWGSRÞ
CH4 þ H2 O $ 3H2 þ CO DH ¼ þ206 kJ=mol
S þ H2 $ H2 S DH ¼ 20:6 kJ=mol
Second: The deviation from equilibrium was estimated through
a quasi-equilibrium model, which allows correcting equilibrium
temperatures in reference to: a specific gas composition for a given
carbon conversion. This procedure was described in detail in two
previous papers [32,34].
Unreacted carbon is calculated by a design specification func-
tion, which is minimized to close the carbon balance in the gasifi-
cation section to less than 5% of relative difference:
h i
MIN ¼ ðCin Þ2  ðF CO þ F CO2 þ F CH4 þ F Tar þ Cu Þ2
Here, Cin, is the inlet molar flow of carbon (kmol/h) and Cu is the
unreacted carbon (kmol/h) in the gasification unit. F i¼CO;CO2 ;CH4 ;Tar
are the molar flows of carbon oxides, methane and tars (naph-
thalene as model compound).
Gas cleaning: This section includes physical and chemical clean-
ing stages namely: cyclone (GS-08), a heat recovery steam genera-
tor (GS-10) and a filter (GS-11). The cyclone is used to eliminate
particulate materials of Dp < 10 lm at 80% of efficiency. The heat
exchanger adjusts the temperature to filter operation. The filter
is designed to fulfill >98% separation of solids (ash) and alkali,
the remaining is retained in the bottom ash. In addition, a conver-
sion reactor (GS-09) is used to quantify the recoverable heat from
unreacted carbon. Details on blocks functions, specifications and
associated FORTRAN subroutines are presented in Supplementary
material (Table S1).
667
4.1.2. Model calibration
The model was calibrated against experimental data reported for
air gasification of various bio-based materials and different reactor
configurations, such as Bamboo (Downdraft) [23], Gulmohar
(Downdraft) [23], Neem (Downdraft) [23], MSW (Fluidized bed)
[3,4], Wood pellets (Fluidized bed) [26], Pine sawdust (Fluidized
bed) [27] and Eucalyptus (Downdraft) [28]). The quasi-equilibrium
calculation was performed under the same conditions as 33 data
sets. Main variables used for validation were the equivalence ratio
(0.2 < ER < 0.5) and gasifier temperature (500 °C < T < 900 °C).
Compositions in Fig. 3 are calculated in dry basis and in some
cases, excluding nitrogen (values above 38%). The correlation coef-
ficient (R), between model and experimental data points, has a
value of 94.17% and it was calculated according to the following
equation:
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u N
uX
u ðy 2
u model;i  yexperimental;i Þ
t n¼1
R¼ ; i ¼ H2 ; CH4 ; CO;CO2 ð2Þ
N
The desired precision (R > 90%) for predicting H2 and CO composi-
tions was reached by restricting the equilibrium temperatures of
R.6 and R.5 [16,22]. It was assumed that, methane is formed during
first devolatilization stages and remained stable to high tempera-
ðR:1Þ
tures. As shown in Fig. 3, calculated compositions of H2 and COx
in the synthesis gas, fit the experimental data with less than 2% of
ðR:2Þ difference; except for the values reported in Chen et al. [24] (red
points), for which larger differences were found: i.e. 6.13–9.35%
ðR:3Þ for H2, 8–8.5% for CO and 9.18–14.25% for CO2. The deviation is
attributed to the high content of ash in the feedstock, which made
difficult to adjust the carbon balance. These results confirm that the
ðR:4Þ
model can be applied with a high level of confidence in the evalua-
tion of biomass gasification systems, provided that carbon balance
for feedstock with high ash content is carefully controlled. Detailed
ðR:5Þ data for model validation, namely gas compositions as a function of
temperature and equivalence ratio are provided in Supplementary
ðR:6Þ material (Supplementary validation gasifier.xls).
ðR:7Þ 4.2. Methanol plant. Models description
Methanol is produced by the catalytic hydrogenation of carbon
oxides (R.8), (R.9), typically over copper, zinc oxide catalysts
(Cu/Zn/Al2O3) [38–41]:
ð1Þ
Fig. 3. Correlation between syngas composition from quasi-equilibrium model and
experimental data values. Red points are for municipal solid wastes [25].
0.2 < ER < 0.5, 500 °C < T < 900 °C. (For interpretation of the references to color in
this figure legend, the reader is referred to the web version of this article.)
668 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
CO þ 2H2 $ CH3 OH DH ¼ 90:77 kJ=mol ðR:8Þ
CO2 þ 3H2 $ CH3 OH þ H2 O DH ¼ 49:16 kJ=mol ðR:9Þ
Reaction R.8 is considered the primary route for Methanol pro-
duction. It has been demonstrated that a small concentration of
CO2 in the feed (2–10%) acts as a promoter and helps stabilizing
the catalyst activity [42]. Nevertheless, lower levels of CO2 can also
promote the Bouduard reaction with the consequent catalyst deac-
tivation due to carbon deposition. Therefore, reaction R.9 is also
included in this study. Reactor temperature (220–280 °C), pressure
(50–100 bar) and the stoichiometric number (SN) (Eq. (3)), are the
main operational variables in Methanol synthesis.
H2  CO2
SN ¼ ; H2 ; CO; CO2 are the molar fraction in syngas
CO þ CO2
ð3Þ
In order to maximize efficiency and yield in the reactor, stoi-
chiometric number should be close to 2.0–2.1. Since, for this study,
the synthesis gas comes from the gasification of biomass, it does
not match the composition requirements (SN), then it must be con-
ditioned before entering the Methanol synthesis loop (MSL) [14].
Therefore, reaction loop represented in Fig. 4, includes the gas con-
ditioning, Methanol synthesis and purification sections.
The modeling was carried out under the following approxima-
tions: (i) steady state calculations, (ii) thermodynamic properties
are estimated using the Redlich–Kwong–Soave (RKS) equation of
state, (iii) negligible pressure drop in heat exchangers, (iv) syngas
compression is evaluated through an isentropic model with
inter-cooling, water extraction and specific efficiency values, (v)
gas conditioning is carried out in WGSR and PSA systems, (vi) equi-
librium reactor.
4.2.1. Operation models
Water gas shift reaction: The objective of this stage is to adjust
the stoichiometric number to match the synthesis requirements
(ideally SN = 2.0) of the Methanol reactor [43]. The extent of WGSR
depends on the producer gas composition and hence on the feed-
stock and gasification conditions. The most important parameters
in the operation of WGSR are the steam to carbon ratio (S/C) and
reactor temperature. According to Haldor Topsoe [43], the S/C
should be above 0.4 to avoid the deposition of carbon on the cata-
lyst surface. In the present paper, this stage was simulated as equi-
librium reactor (SL-01) running between 250 and 350 °C and at
atmospheric pressure. This model integrates both phase and chem-
ical equilibria to estimate a product composition. Moreover, S/C
Fig. 4. PFD of Methanol synthesis loop.
ratio was controlled between 0.4 and 0.5 by varying the steam flow
to the reactor (S18) in a design specification block. Details on reac-
tor model and FORTRAN codes are provided in Supplementary
material (Table S2).
Gas upgrading: Upgrading of the gasification gas aims to elimi-
nate sulfur compounds and control CO2 levels. Usually, sulfur
removal is either done by a zinc oxide filter (as with natural gas)
with COS hydrolysis upstream to convert COS to H2S or by a scrub-
ber with amines [15,43]. On the other hand, CO2 is commonly
removed by using absorption technologies such as: Rectisol,
Selexol and MEA/MDEA systems [11,14,44]. These processes oper-
ate at low temperatures (25–60 °C) and moderate pressures
(<30 bar). Other alternative could be the pressure swing adsorption
(PSA), which has proven to be an efficient and economical way to
purify hydrogen. Gutiérrez-Ortíz et al. [42] reported the applica-
tion of PSA for the adjustment of SN in a novel process for Metha-
nol synthesis. In the present paper, the gas upgrading stage was
simulated as a separator block (SL-02), with specific CO2 outlet
composition (6% mol). Energy consumption was calculated on the
basis of the data reported by Gutierrez-Ortiz [42].
Compression of synthesis gas: The selection of the exact pressure
to run the Methanol synthesis loop will depend on an OPEX/CAPEX
optimization [35]. In this study, the synthesis gas is compressed to
50 atm in a multiple stage compressor (SL-03) with inter-cooling
and water decantation systems. The exit temperature of the com-
pression train was fixed at 125 °C for a constant stage pressure
ratio of 1:10. The compression stage was simulated using a isen-
tropic block and considering 85% of isentropic efficiency and 3%
mechanical losses. Coolers/decanters were simulated as flash units
for which phase equilibria was solved along with mass and energy
balances. In Fig. 4 (highlighted section), the acronyms Ci refers to
decanted water in the compression train. Further details on the
modeling can be found in Supplementary material (Table S2).
Methanol synthesis: Methanol synthesis loop was modeled by
using various unit operation blocks (SL-04 to SL-10). The com-
pressed syngas was preheated to a specific reactor temperature
(220–270 °C) in a heat exchanger (SL-04). Lower temperatures lead
to slow reaction rates, and above 280 °C, the catalyst may lose
activity by surface sintering. The composition of the product gas
was estimated in an equilibrium reactor (SL-05), by considering
main synthesis reactions (R.8) and (R.9) and the WGSR (R.5). The
WGSR was included because most of catalysts for Methanol syn-
thesis have also shown activity for this reaction, which may
account for their ability to synthesize Methanol from either CO
or CO2 [42]. The equilibrium model allows estimating the crude
Methanol composition by solving phase and chemical equilibria
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678 669

along with mass and energy balances. In further analyses, an activ- reverse carbon gasification reaction (R.3), leading to catalyst deac-
ity coefficient will be introduced to study the influence of catalyst tivation. To avoid these undesirable reactions, levels of steam at
on process economy. Thereafter, products from reactor are the first reactor inlet and H2/CO ratios should be controlled.
expanded in a valve (SL-06) to 25 atm, cooled to 25 °C (SL-07) The SNG concept applied in this paper (Fig. 5) is based on the
and after that condensate (crude Methanol) is separated from the steam-moderated ICI once-through methanation process, reported
unconverted gas in a gas–liquid separator (SL-08). A fraction of by Mozaffarian et al. [9], Kopyscinsky et al. [7] and Vitasari et al. [6].
the gas stream (S33) is recycled to the reactor in order to increase This technology converts the syngas into a methane rich stream
Methanol yield, while crude Methanol (S31) is sent to the purifica- using a series of adiabatic fixed bed catalytic reactors (SNL-02,
tion section. SNL-04, SNL-06,). As a special feature, this reaction system can han-
dle gases with high content of CO at high temperatures.
4.2.2. Methanol purification The PFD includes the syngas conditioning, SNG cleaning and
Purification of Methanol is commonly performed in a distilla- power production from superheated pressurized steam. Approxi-
tion system as crude Methanol usually contains water and small mations to simulate the SNG loop are: (i) steady state calculations,
fractions of dissolved gasses. This section was modeled using a (ii) thermodynamic properties are estimated using the Redlich–
valve (SL-11) to expand the mixture up to 3.5 atm and after that Kwong–Soave (RKS) equation of state, (iii) pressure drop in heat
the mixture is heated (SL-13) to the column inlet temperature exchangers is negligible, (iv) isentropic model was assumed for
(mixture at its bubble point 100 °C). The gaseous species are Syngas and SNG compression and in steam turbine, (v) equilibrium
flashed out in an adiabatic flash separator (SL-13) and the remain- reactor.
ing boiling liquid is fed into a distillation column (SL-14). Number
of theoretical stages, distribution of non-keys between the over- 4.3.1. Operation models
head and bottoms products, reboiler and condenser duties, mini- Syngas compression: The gas compression to 25 atm, was mod-
mum and operating reflux ratios and location of feed stage, eled in a single stage compressor (SNL-01), using an isentropic
among other design parameters of the distillation column, are esti- model and the same assumptions as above described for the
mated by using the shortcut design method (Fenske–Underwood– Methanol synthesis loop.
Gilliland) [45]. Specifications for each block and the corresponding SNG reaction train: Operation temperature is critical for the SNG
modelling approaches are given in Supplementary material reaction train. Therefore, this variable should be controlled (SNL-
(Table S2). 02 to SNL-06) in a way that favors the equilibrium of methane for-
mation. Same temperature levels as reported by Vitasari et al. [6]
and Mozaffarian et al. [9], were considered, namely: 1st stage feed
4.2.3. Model calibration
398 °C and product 729 °C, 2nd stage feed 325 °C and product
In order to examine the model accuracy for studying Methanol
590 °C, 3rd stage feed 300 °C and product 428 °C. System pressure
synthesis, the data reported in Xiang et al. [41] referred to indus-
was fixed at 25 atm and the pressure drop through the reactor sys-
trial Methanol facilities installed in Shangai Coking and Chemical
tem at 1.5 atm. Stoichiometry H2/CO ratio at the reactor inlet
Co. was adopted as reference case (Factory in Table 3).
should vary between 2.5 and 3.3. A cluster of three heat exchangers
As shown in Table 3, relative deviation between modeled
(SNL-03, SNL-05, SNL-07) is used to decrease the temperature of
Methanol composition and industrial data are below 5%. These cal-
gas stream before it is fed into the next reactor, and to produce
culations are equilibrium-based; due to this, Methanol fraction is
superheated steam (S57). Heat exchange is supposed at counter-
slightly overestimated. Nevertheless, the results allows stating that
current and pressure drop through tube bundle is assumed negligi-
the model is suitable for process synthesis calculations.
ble. Superheated steam is sent to a steam turbine (SNL-10) to fulfill
power requirements for compression and/or pumping.
4.3. Synthetic Natural Gas. Models description SNG purification: Reactor products are enriched in methane, but
also contains water and CO2. Water is formed from R.10 and R.11
Methanation is the main reaction in the production of SNG; it and also is fed into the reactor (steam in stage 1) to control the
takes place when carbon monoxide and carbon dioxide are con- temperature profile. CO2 enters in the syngas stream (-S23). The
verted to methane according to the following reactions: water content of the SNG is reduced in a flash separator (SNL-08)
at 25 °C and 5 atm. Then, dry SNG is compressed (SNL-09) to
CO þ 3H2 $ CH4 þ H2 O DH ¼ 206 kJ=mol ðR:10Þ
50 atm and sent to a CO2 separation unit where clean SNG is pro-
duced (90% CH4). Separation of CO2 could be done under the
CO2 þ 4H2 $ CH4 þ 2H2 O DH ¼ 165 kJ=mol ðR:11Þ same conditions described above for SL-02. Specifications for each
Group VIII metals catalyze this process, among which nickel has block and the corresponding modelling details are given in Supple-
proven high activity and selectivity to methane formation. Besides mentary material (Table S3).
reactions R.10 and R.11, the operational conditions can promote
the formation of carbon through Boudouard reaction (R.2) and 4.3.2. Model calibration
Model for SNG was calibrated using the experimental data
reported by Kopyscinski [7] for an ICI methanation process. Same
Table 3 feeding conditions as Kopyscinski [7] (syngas composition and
Results of model calibration for Methanol synthesis loop. temperature) were used in the first stage. Results of calibration
T (°C) P Feed gas composition (% Methanol (% mol) are summarized in Table 4.
(atm) mol) Model correlation coefficients (R2) were above 99% validating
H2 CO CO2 N2 Factory Model Rel. Dv.* its reliability to forecast the effect to analyze process integration
[41] (%) alternatives.
251.8 44.9 67.19 29.5 2.92 0.33 94.75 97.71 3.1
256.5 47.3 67.71 28.91 2.75 0.56 94.52 97.62 3.3 4.4. Heat integration
260.4 46.9 67.6 29.48 2.51 0.35 95.59 97.81 2.3
264.45 46.7 68.23 28.82 2.54 0.36 94.95 97.75 2.9
The overall energy efficiency of systems depends on their inte-
*
Relative deviation = (Factory  Simulation)/Factory * 100%. gration degree. Several studies have been focused on this issue, and
670 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678

Fig. 5. PFD of the SNG synthesis loop.

Table 4 all of them define the integration as a mandatory step for process
Model calibration. design [13,39]. Therefore, in this study, the opportunities for
1st methanator 2nd methanator 3rd methanator energy savings within systems are explored through the PINCH
Inlet Outlet Inlet Outlet Inlet Outlet methodology, which have been reported as a method suitable to
Temp (°C) 398 729 325 590 300 428 identify the opportunities for saving energy in a system [31,46,47].
Experimental values [7]
The method is applied in two general steps:
Composition (vol %)db
H2 42.9 35.5 35.5 20.3 20.3 5.8  A targeting phase that aims identifying minimum energy
CO 31.1 14.5 14.5 4.3 4.3 0.3 requirements of the system by considering the heat recovery
CO2 24.7 40.2 40.2 53.9 53.9 62.7
between hot and cold streams.
CH4 0.1 8.5 8.5 19.8 19.8 29.1
N2 1.2 1.4 1.4 1.7 1.7 2  Design of the heat exchanger network (HEN).
Calculated values
Composition (vol %)db In this study, thermal integration was carried out for three
H2 42.9% 36.4% 36.4% 20.6% 20.6% 5.8% cases: (i) Gasification plant integrated to Methanol synthesis loop
CO 31.1% 14.5% 14.5% 4.2% 4.2% 0.3% (G-MSL), (ii) Gasification plant integrated to SNG synthesis loop
CO2 24.7% 39.8% 39.8% 53.7% 53.7% 62.7%
(G-SNG), (iii) Gasification plant integrated to both Methanol and
CH4 0.1% 8.0% 8.0% 19.7% 19.7% 29.2%
N2 1.2% 1.3% 1.3% 1.6% 1.6% 1.9%
SNG synthesis (G-Integrated).
Base case simulations for the systems under analysis (Fig. 2, 4
Avg. R2 (%) 99.9 99.9 99.9
and 5) were used to calculate mass and energy flows for hot
SNG synthesis loop. and cold streams, identifying this way heat sources and sinks,

Table 5
Assumptions for the economic analysis.

Plan section Reference size Cost (€) Cost factor Year Source
Biomass drying 50 ton/h 7500 540€/(kg/s)evap 2010 [15]
Gasification and cleaning 30 MWth 495,441 16,514€/MWth 2010 [15]
Methanol synthesis 17 kmol/s (syngas feed) 267,000 16,000€/(kmol/s) 2010 [15]
Distillation 85 kg/s (feed) 267,000 3100€/(kg/s) 2010 [15]
Synthetic Natural Gas 1 kWth 593
Heat exchanger network 9 < area < 500 m2 1632 * (A)0.6375 2009 [47]
for area < 9 m2 1066 * (A)0.075
Feedstock and utilities
Pine chips (MC: 35–40%) 1 ton 43 [2]
Steam 1 kJ 1.9 * 104 [48]
Cooling water 1 kJ 1.9 * 105 [48]
Electricity 1 kJ 5.2 * 105 [48]
Assumptions
Dollar exchange rate 1.13 USD/€
Financing mechanism 100% via debts
Interest rate 6%
Discount rate 10%
Maintenance cost 5% year
Number of years 20
Operators salary 6800 €/year
N° operators 8/shift*
Plant availability 90%
Scale up law Eq. (4)
Marshall and swift index (MI) 2013 593.8
*
Full time operation requires 3 shift per day.
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
respectively. Thereafter, the temperature-enthalpy profiles
(composite curves) of such streams were used to determine the
potentialities for heat exchange between process streams and to
calculate the minimum utility requirements (MER). The cumula-
tive enthalpy curve (Grand Composite Curve) is then obtained
and considering temperature levels and heat availability, several
alternatives for utilities generation/usage are proposed. Aspen
Energy Analyzer v8.6 was used to obtain the Composites curves
(Hot and Cold) and Grand Composites Curves (GCC) at a minimum
temperature approach (DTmin) of 10 K [39]. The total cost determi-
nation of the HENs is based on minimum energy and area
requirements.
4.5. Economic evaluation
Simulation results of Gasification-SNG, Gasification-Methanol and
Integrated Gasification-SNG-Methanol, are used to estimate the eco-
nomic feasibility of processes. Once most feasible operation condi-
tions were obtained in the flowsheet model, the sizing of major
equipment in the system was carried out. With these results,
investments and operation costs are determined using the refer-
ence data reported in Table 5. Cost of feedstock was calculated
based on of regional market values for pinewood.
 0:7
MIactual Actual Size
Cost ¼  Reference Cost o ð4Þ
MIreference Reference Size
Furthermore, sensitivity analyses on several parameters affecting
the economic feasibility of the studied processes are included.
5. Results and discussion
The models described in preceding sections are used to study
the effect of operational parameters on biomass gasification,
Methanol and SNG synthesis, and to perform the heat integration
of systems. Those analyses are the basis to estimate the economic
feasibility of biomass gasification-to-SNG/Methanol production.
Reported mass and energy balances are for a processing capacity
of 1000 kg/h of P. radiata.
5.1. Gasification
The gasification section represented in Fig. 1 was studied at
500 < T < 900 °C and 0.15 < ER < 0.5. Main outputs of the model
are:
U Syngas composition (mainly H2, CH4, COx) and Lower Heating
Value (LHV).
U Heat load for gasification.
U Stoichiometric number in crude gasification gas.
The ER was calculated based on the complete combustion of
pine, by deducing a hypothetic chemical equation as presented in
Arafat et al. [49]. The heat load in gasifier was calculated by consid-
ering the in situ conversion of tars. Tar was represented with a
model compound (naphthalene) and the heat of reaction was cal-
culated for the following stoichiometric equation:
C10 H8 þ 12O2 $ 4H2 O þ 10CO2 DH ¼ 5100 kJ=mol ðR:12Þ
5.1.1. Effect of gasification temperature
The components profiles shown in Fig. 6 resulted from
heterogeneous decomposition, oxidation and reforming reactions
(R.1–R.7).
As temperature increases, char and tars are cracked into more
simple molecules, while carbon conversion is favored (Boudouard
671
Fig. 6. Effect of gasification temperature on syngas composition (dry, N2-free basis)
during P. radiata gasification. ER = 0.30.
reaction R.2) [28,50,51]. This statement is evidenced by the propor-
tional increment in CO molar fraction as well as by a reduction in
the partial pressure of CO2. The increment of CO composition and
the slight reduction in hydrogen concentration above 700 °C, could
be attributed to the combination of reverse WGSR (R.5) with
methane steam reforming [28,32]. At the studied conditions the
SN of producer gas was too low (0.31 < SN < 0.36). Therefore, it
should be increased in further conditioning stages, to fulfill the
minimum requirements of Methanol and SNG synthesis loops
(SN  2.0). The LHV sharply increases with temperature until
850 °C (3.91 MJ/kg), from this point it starts forming a plateau. This
tendency has also been reported by Li et al. [23] and Gómez-Barea
[52] and could be related to the equilibrium of fuel gases (i.e. H2 and
CO). Similarly, above 700 °C, the effect of hydrogen oxidation
(LHVH2 = 120 MJ/kg) on the LHV is partially compensated by the
formation of CO (LHVCO = 10.1 MJ/kg). On the other hand, the gasi-
fier was characterized by a stepwise increment of the heat con-
sumption from 1.27 MWth at 600 °C to 1.71 MWth at 900 °C, at an
average rate of 1.7 kW/°C. When the gasification system is operated
above 800 °C, the heat recovery potential in the steam generator
(SG-10) is up to 526.7 kg/h of superheated steam (350 °C, 3 atm).
Based on the above discussed results, it can be inferred that
working between 800 and 850 °C could favor the use of gasification
gases in combustion and chemical synthesis applications
[12,25,32,42,53].
5.1.2. Effect of equivalence ratio
The equivalence ratio is a determinant parameter for gasifica-
tion processes, as it influences the producer gas composition, reac-
tor temperature (autothermal operation) as well as the overall
process efficiency [25,32,42,53]. In this study, the ER was investi-
gated between 0.15 and 0.5 (at constant temperature). The value
of ER was determined using an approximated chemical formula
(C4.1H6.9O2.7N0.01) for biomass (P. radiata), using the data reported
in Table 2.
The change of gas composition and its heating value as a func-
tion of ER is reported in Fig. 7. On one hand, the ER necessarily pro-
duces a proportional effect on oxidation reactions (R1 and R2) and
hence on the composition of fuel gases (CH4, CO, H2). This effect
can be seen for ER between 0.2 and 0.5, where the concentration
of H2 and CO decreased from 43% to 25% and 44.9% to 30%, respec-
tively. This caused a reduction in the gas quality (LHV) to a mini-
mum of 1.6 MJ/kg at ER = 0.5. This influence of augmenting O2
stoichiometry supply on the oxidation reactions can be verified
by the proportional increment in the CO2 concentration from 8%
to 41%. A similar result was reported by Gómez-Baera [52], which
672 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
Fig. 7. Effect of equivalence ratio on syngas composition (dry, N2-free basis) during
P. radiata gasification. T = 850 °C.
found an increment from 60% to 100% in char conversion by chang-
ing ER from 0.2 to 0.3. On the other hand, the ER also affects the
gasification temperature, under the condition of autothermal oper-
ation (heat is self-provided by in situ biomass oxidation). The
higher the ER induced higher gasification temperatures, which
favors the rate of reactions and the gas quality to a certain point.
Therefore, a tradeoff is established between product quality and
gasification temperatures, mostly when reactors are operated at
autothermal regime. According to the above explained, a feasibility
region for ER is identified in this study, which is limited by gas
composition, gasifier efficiency and the stoichiometric number of
the producer gas. At ER < 0.2 the SN was 0.83; but carbon conver-
sion was below 90%, making the operation in this range unfeasible.
Above ER = 0.3, the composition of gasification gas becomes more
similar to a combustion gas (CO2 > CO > H2) reducing its potential-
ities for downstream applications (See LHV profile). Accordingly,
the gasifier may be operated at 0.2 < ER < 0.3 to guarantee a syngas
LHV able to feed lean combustion ignition systems and an accept-
able SN (>0.65) for further synthesis applications. At this condition,
the cold gas efficiency varies between 69% and 74%.
5.2. Gas conditioning
The gas conditioning section is simulated by an ideal separator
but using realistic values for pressure and temperature from
Gutiérrez-Ortíz et al. [42]. The PSA is simulated to produce a
stream (S22) with 95% of CO2, and a mixture (S23) of H2, CO and
other gases from gasification section. The level of CO2 purity was
fixed based on the specification for transport and sequestration
of CO2. Results from this stage is implicit in the mass and energy
tables for both: Methanol synthesis and SNG loops.
5.3. Methanol synthesis loop
The feasibility of using syngas from P. radiata gasification for
Methanol production is studied in this section. Typical operation
temperatures (220 < T < 270 °C) and pressures (50 < P < 80 atm)
for Methanol synthesis are explored. Since the Methanol synthesis
is an exothermic reaction (R.8) and (R.9), the selection of the oper-
ating temperatures is subjected to a compromise between reaction
rate and equilibrium shift, while pressure is defined by reaction
equilibria (favored at higher values) and power consumption in
the compression train. Moreover, it has been reported that at high
temperature (above 270 °C), the catalyst suffers sintering which
leads to a decreases in the active surface area [54].
The effect of recycle/purge fraction (R/P) on Methanol synthesis
was also evaluated, because it could significantly affects the partial
pressure of reactants in the feedstock by purging inerts (specially
N2 and CO2) and also it is related to the reactor size [39]. The R/P
is defined as the ratio between molar flow of the recycled stream
to the molar flow of purged stream (S30).
Therefore, the model for Methanol synthesis loop represented
in Fig. 4 was used to study the effect of temperature, R/P and pres-
sure on:
U Syngas composition (stoichiometric number).
U Carbon oxides conversion.
U Methanol selectivity
 
F out in
ðMeOHÞ  F ðMeOHÞ
SMeOH ¼ l   m : ð5Þ
F in out in out
ðCOÞ  F ðCOÞ þ F ðCO2 Þ  F ðCO2 Þ
U Compressor power consumption.
U Number of stages, heat duties and recycle ratio for Methanol
distillation.
5.3.1. Effect of reactor temperature and pressure
Temperature, pressure and R/P were used to decide the opera-
tional point for further analyses. Table 6 summarizes the results
for temperature and pressure.
Assuming that synthesis of Methanol takes place at equilibrium
and based on the Le Châtelier’s principle, it can be inferred that
Methanol production is favored at low temperatures and high
pressures [15,40,43]. Results in Table 6 corroborate the previous
statement. In addition, Methanol molar fraction in products (previ-
ous to purification) varies between 78.4% and 89.1%, which is in
well agreement with the data reported by Rongard [43] for an inte-
grated gasification – Methanol plant using torrefied biomass as
feedstock. In the same line, Abrol and Hilton [55] and Gutierrez-
Ortiz [42], reported near 89% of Methanol molar concentration
for a syngas of similar composition and derived from an intermit-
tent biomass-gasification process running on solar energy.
Methanol selectivity was between 0.99 and 1 for all the studied
cases and carbon oxides conversion was favored by equilibrium. In
the case of CO2, the negative values for conversion, represent the
reverse equilibrium.
Neither temperature nor pressure in the reactor affected the
number of theoretical stages in the distillation column. Neverthe-
less, heat duties in reboiler and condenser are reduced at expenses
of a lower production of Methanol. At 220 °C and 50 atm Methanol
production yield (0.59 kgMeOH/kgDry Biomass) and carbon conversion
(87.5%) are rather good. At higher pressures, this value is slightly
increased, but operation at such a pressure levels may imply higher
specific CAPEX/OPEX costs.
5.3.2. Effect of recycle/purge ratio
The recycle of a fraction of products in Methanol synthesis pro-
cess is commonly carried out to increase the carbon oxides conver-
sion per-reactor pass. In order to reduce the accumulation of inerts
in the reactor, purge of a fraction of the recycle is performed. In the
present paper, a broad range for R/P was chosen to study its effect
on Methanol yield (Eq. (6)) and process economy respectively
[39,42,55,56]:
F MeOH
Y MeOH ¼  100 ð6Þ
FB
where YMeOH is the mass yield of Methanol (%), FMeOH is the mass
flow of Methanol (98%) produced in the distillation column (kg/h)
and FB is the flow of biomass fed to the gasification section (kg/h).
Methanol production varied from 31.95% to 44.61%
(0.13–0.22 kgMeOH/kg-gas) within the studied interval, which is
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678 673

Table 6
Effect of temperature and pressure on Methanol synthesis loop.

Temperature (°C) Pressure (atm)

220 230 240 250 260 270 30 40 50 60 70 80
Reactor
Stoichiometric number 1.79 1.80 1.81 1.82 1.83 1.84 1.832 1.81 1.79 1.82 1.81 1.81
CO conversion (%) 87.5 82.1 75.3 67.1 58.0 48.6 76.6 83 87.5 90.5 92.6 94
CO2 conversion (%) 0.40 0.75 1.6 2.4 2.9 3.3 6.6 2.9 0.4 2.9 2.2 1.7
Distillation
MeOH in feed (% mol) 82.28 82.86 83.31 83.56 83.51 83.09 78.4 81.1 82.3 87.1 88.2 89.1
Number of stages 22 21 21 21 21 21 22 22 21 21 21 21
Feed stage 12 12 12 12 12 12 13 12 12 12 12 12
Min. reflux ratio 0.62 0.61 0.61 0.602 0.60 0.61 0.68 0.64 0.62 0.56 0.55 0.54
Heat duty condenser (kW) 401 389 376 359 340 317 227 252 268 243 246 248
Heat duty reboiler (kW) 113 111 108 104 98 91 89 104 113 112 115 117
Power for compression (kW) 459 459 459 459 459 459 369 418 459 494 524 551
Selectivity 0.99 0.98 1.00 1.00 1.00 0.99 0.99 0.98 0.99 0.99 0.99 1.00

R/P = 5.

very promising, considering that Zhang et al. [57] obtained
0.356 kgMeOH/kg-gas, but using syngas from steam reforming of
natural gas.
Fig. 8 shows the proportional effect of R/P on YMeOH and on the
cost related to the recycling systems (compressor and heat exchan-
ger). When more than 80% of the recycle stream is fed into the
reactor (R/P > 5), the YMeOH starts to form a plateau, which can be
explained by the approach to the equilibrium for reactions R.8
and R.9. Higher recycle do not further favor the process. Neverthe-
less, at such a high R/P, the reactor size should augment to main-
tain residence time and the recycle compressor-heat exchanger
should manage higher flows. Therefore, the operation costs of the
recycle loop will grow. Accordingly, the feasibility boundaries for
R/P should be defined by a compromise between the desired
Methanol yield and the costs associated to the recycle system.
5.4. SNG synthesis loop
The effects of pressure and first reactor temperature on the SNG
loop were investigated. Both variables influenced the rate of
methane formation reaction and the energy balance of the system.
Table 7 summarizes the effect of the investigated operation vari-
ables on mass and energy balances for the SNG Loop.
The content of CH4 in the SNG (highlighted area in Table 7) pro-
duced from biomass gasification, varied between 88.2% and 88.5%.
The calculated CH4 composition of the SNG is similar to that
reported by Molino and Braccio [58] (80%), Li et al. [59] (94.5%
for syngas from coal gasification) and to the DOE report for gasifi-
cation gases applications [60].
As shown in Table 7, increasing system pressure and decreasing
first methanator temperature, lead to a positive effect on methane
production and on the conversion of CO in the first reactor (XCO-1R).
Methane molar fraction (on wet basis) at the exit of the first
methanator varied between 0.179 at 500 °C and 0.083 at 729 °C,
which is similar to that reported in Gröbl et al. [18] for an inte-
grated steam biomass gasification – one stage SNG system. These
results arise from the chemical equilibrium principles [6,58] and
can be quantified using a yield plot (Fig. 9); here yield is defined
as the molar flow ratio between CH4 in the product stream (S42)
and CO in the feedstock (S41). Usually, the temperature of the first
reaction step in methanation is constrained by the catalyst thermal
stability and it can vary between 600 °C and 750 °C [58]. For fur-
ther analyses, 650 °C and 25 atm are used. These conditions corre-
spond to the 64.97% XCO-1R, 65% first reactor yield and 581.05 kW
of heat to be removed (feasibility region in Fig. 9). Lower temper-
atures will limit the reaction rate, increasing the residence time
and reactor size, while operation above 650 °C will decrease CH4
concentration and is prone to catalyst deactivation by coke deposi-
tion and sintering [58].
The global yield given as kg of SNG per kg of dry biomass fed
into the gasifier, varied between 0.32 and 0.33, which is higher
than those reported by Vitasarai et al. [6]. Regarding the steam

Fig. 8. Effect of recycle to purge ratio on Methanol composition and final production.
674 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
Table 7
Effect of pressure and temperature on mass and energy balances for SNG Loop.
and power production, this system can provide up to 14.28% of the
total power requirements in the plant (1464 kg/h of steam and
104 kW).
5.5. Heat integration
The opportunities for energy saving are evaluated by a PINCH
analysis. Energy targeting is carried out at best performance condi-
tions, simulated in the preceding sections. Streams data are gath-
ered from the simulation results of the PFDs described in Figs. 2,
4 and 5. Table 8 summarizes the information of all the streams
included in the PINCH analysis.
The minimum energy and area requirements for the integrated
system (G-Integrated) were calculated by varying gasification sec-
tion capacity to guarantee the same flow of syngas to the SNG and
Methanol production plants. Main results of the targeting are pre-
sented in Table 9. The information related to heat integration is
considerably expanded in Supplementary material (Heat Integra-
tion.xls), where details on data extraction, composite curves and
heat exchanger network design are provided.
Data in Table 9 are used to analyze the potential heat integra-
tion alternatives and the possibilities to generate services along
with the main products. At the studied conditions, heat load for
gasification (1700 kW) is, by far, higher than any other heat
requirements. This heat must be supplied by a high temperature
source (direct heating) – usually through the combustion of the
biomass itself – or by an external heating (hot utility).
Fig. 9. Effect of reaction temperature and pressure on first reactor yield.
Based on the trend of GCC (Fig. 10), both synthesis loops could
be classified as heat sources, as consequence of the exothermic
character of the reactions involved (R.5), (R.8)–(R.10). Therefore,
this heat availability must be recovered to increase the energy effi-
ciency and to avoid exergy losses. As shown in Fig. 10, there is a
clear similitude in the energy trend for both: Gasification-
Methanol and Gasification-SNG, operating in standalone mode.
Nevertheless, a higher availability of heat below the pinch
(2061.04 kJ/h) is found for SNG, due to the higher exothermic
behavior of the reaction train as compared to the Methanol reactor.
Therefore, this alternative is prone to be integrated with a cogener-
ation scheme (Blue lines in Fig. 10). Cooling requirements can be
exploited to create a steam generation network with three levels
of pressure (HPS, MPS, LPS), aimed to feed a steam turbine
(104 kW net power) as shown in Fig. 5. Moreover, the products
from first stage methanator and producer gas could be used to
superheat the steam.
The effect of such an integration is reflected on the utilities and
total area requirements (39.1% higher than standalone MSL and
45.3% for standalone SNG). The co-produced steam for the inte-
grated plant (1964.49 kg/h), can be used to fulfill the requirements
for WGSR (210.61 kg/h) and, steam drying of biomass from 30% to
10%. On the other hand, has been demonstrated that varying oper-
ating conditions (in the reaction systems) affects the global energy
targeting in a lesser degree [10]. Accordingly, the annual cost of
heat exchanger network is more sensible to the purchase cost than
the operating cost, hence it should be designed based on minimum
area requirements.
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678 675

Table 8
Process and stream table for heat integration.

Processes conditions? Gasifier Methanol synthesis Methanation

T = 850 °C, ER = 0.3 T = 220 °C, P = 30 atm, R/P = 5 T 1st reactor = 650 °C, P = 50 atm
Streams summary
Description Equipment ID Stream ID Ts (°C) Tt (°C) C (kW/C) Q (kW) Type
Gasifier GS-03 + GS-05 S6 849 850 1700 1700 Cold
Dryer GS-01 S03 20 120 1.21 121.43 Cold
Air preheater GS-04 S06 15 100 0.53 45.05 Cold
Gas cooler GS-07 S09 849 700 1.26 187.016 Hot
HRSG GS-10 S011 700 300 1.18 470.84 Hot
WGSR SL-01 S017 320 300 4.62 92.4 Hot
Methanol reactor SL-05 S25 221 220 357.270 357.27 Hot
1st stage compressor SL-03 S24 125 220 0.98 93.47 Cold
2nd stage compressor SL-03 S21-1 863 125 0.60 443.75 Hot
3rd stage compressor SL-03 S21-2 220.6 125 1.32 126.42 Hot
4th stage compressor SL-03 S21-3 179.7 125 1.00 54.39 Hot
5th stage compressor SL-03 S21-4 163.4 125 0.81 31.21 Hot
Product cooler SL-07 S21-5 154.6 125 0.72 21.4 Hot
Distillation condenser SL-14-COND S39 127 99.32 9.67 267.73 Hot
Distillation reboiler SL-14-REB S40 107.1 127.1 5.65 113.049 Cold
Distillation preheater SL-13 S36 24 107.1 2.31 191.82 Cold
Crude Methanol cooler SL-07 S28 217 25 1.76 338.26 Hot
1st methanator SNL-02 S41 650 398 0.19 61.74 Hot
2nd methanator SNL-04 S43 590 325 0.22 59.03 Hot
3rd methanator SNL-06 S45 428 300 0.07 8.71 Hot
Cooler to reaction train SNL-01 S23 1037 398 0.91 582.03 Hot
1st inter cooler SNL-03 S42 729 325 0.84 340.06 Hot
2nd inter cooler SNL-05 S44 590 300 0.81 234.017 Hot
3rd inter cooler SNL-07 S46 428 35 1.45 570.075 Hot

Table 9 5.6. Economic evaluation

Targeting results.

PINCH parameter Gasification– Gasification– Gasification– Main assumptions for the economic analysis were:
Methanol SNG Methanol–SNG
G–MSL G–SNG G-Integrated - Heat exchanger networks were calculated using the targeting
Minimum hot 1698 1538 3336 results from energy integration.
utilities (kJ/h) - Price for biomass (P. radiata) was based on market values.
Minimum cold 1824 2279 3503 - The base case considered 100 MWth of fuel production capacity.
utilities (kJ/h)
- Interest and discount rates were modeled separately.
Minimum N° 18 14 25
exchangers - Twenty years lifetime.
Minimum area (m2) 52.4 47.1 86.1
Pinch temperature 859/849 859/849 859/849 The capital and unit product costs are presented in Table 10,
along with market values of main products.
Furthermore, Fig. 11(a) and (b) provide a detailed profile of total
capital investment (TCI) and operation costs for the three studied
alternatives. As shown, major impact on product costs comes from
biomass price and utilities, accounting for nearly 50% of the total
production cost. On the other hand, investment costs and working
capital represent 19% and 17% of TCI, respectively. Similar results
were reported by Andersson et al. [11].
Although large number of uncertainties can be identified in
such an economic forecasting, the developed process alternatives
have more promising economic indexes than that reported by
Clausen et al. [15], which could be associated to the lower electric-
ity consumption and biomass prices. The unitary product cost for
Methanol, using the G-MSL alternative (29.54 $/GJ), is 42% higher
than its market value, while for G-SNG it is 3.8 times higher than
natural gas, suggesting that the process is unfeasible. Nevertheless,
these values could be substantially improved by considering the
potential benefits associated to CO2 capture and preferential green
energy taxes for product commercialization. Moreover, as the tra-
ditional economic assessment method has considerable deviations
from the actual situation [62], a sensitivity analysis on different
parameters (operation and economics) influencing on product cost
is required. Therefore, sensitivity analyses for biomass price, capi-
Fig. 10. Grand Composite Curves for the studied cases. SHS-superheated steam, tal cost and processes yield, are included below. Ranges for each
HPS, MPS, LPS-high, medium and low-pressure steam. parameter were defined based on expert criteria and on statistical
676 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678

Table 10
Prices of Methanol, SNG and other reference fuels.

Products Gasification/Methanol-standalone Gasification/SNG-standalone Gasification/SNG/Methanol-integrated

Price/cost
Methanol ($/GJ) 29.54 – 26.74
SNG ($/GJ) – 18.41 16.85
Commercial Methanol ($/GJ; $/L) 20.74; 0.33 https://www.methanex.com/our-business/pricing
Commercial natural gas ($/GJ) 4.89 [15]
Ethanol 2nd generation ($/L) 0.28 [61]
Fixed capital investment (MM$) 151.02 135.27 272

Base case.

Fig. 11. Production cost distribution. Reference data for calculations is based on Tables 6–10.

data gathered from governmental sources (specifically for biomass
market).
It is worth noting that biomass market in Chile is prone to
change, due to the growing interest in its use as fossil fuels substi-
tute for heat and power production [22,63]. Consequently, the
uncertainties associated to forecasting the effect of biomass market
price on systems feasibility are relevant. Therefore, a wide interval
is used to explore this variable, namely 1–60 $/tonne. These values
were selected based on real market prices reported by INFOR [21];
being the lower limit the price of wood residues (sawdust) com-
mercialized by sawmills. Another important problem associated
to the uncertainties in economic evaluation of processes in early
stage of development is closely related to thermodynamics-based
simulations. These calculations leads to an overestimation of pro-
cess yields by considering that reactions takes place at equilibrium
(ideal condition). These approximations result in lower unitary
costs of products than those obtained under real conditions. In this
paper, the deviation from equilibrium in reaction systems (MSL
and SNG) was considered by introducing an approach to equilib-
rium coefficient, C.Actv, (Eq. (7)):
C:Actv ¼ 100  ðXr=XeÞ; Xe; Xr are the equilibrium
real conversion; respectively: ð7Þ
The impact of this coefficient on mass and energy balances as
well as on products yield is evidenced in products cost (Fig. 12(a
and b)). C.Actv. values were varied between two extremes:
Maximum attainable yield (C.Actv = 100%): This is reached at
equilibrium conditions.

Fig. 12. Effect of biomass price and catalytic activity on the unitary energy cost.
 L.E. Arteaga-Pérez et al. / Chemical Engineering Journal 286 (2016) 663–678
Minimum yield (C.Actv = 10%): Assuming that catalysts are
almost deactivated.
Fig. 12(a and b) shows the sensitivity of product costs (energy
based) to the variation of biomass price, plant costs and C.Actv.
Results evidenced the potentialities of using an integrated process
architecture instead of individual production of Methanol and SNG.
The SNG unitary costs remained within the market values for
Methanol and natural gas when biomass prices varied between 1
and 60$/tonne and at C.Actv above 50%. Effect of C.Actv below
40% is critical for the process economy-produced a 60% increment
of unitary costs-, which suggests that regardless of the catalysts
formulation its regeneration cycle should be carried out by consid-
ering this C.Actv as its lower limit. In all the explored scenarios the
G-MSL system operating in standalone condition, does not satisfy
the economic balance, therefore it should be integrated with SNG
in order to improve the economic indicators. This integration
allows reducing utilities (21% of operation costs) by using the heat
available in the process streams for heating/cooling as well as for
power production.
Capital cost was analyzed for two scenarios: positive/negative
with a ±40% of variation, using as baseline the cost estimated
through traditional costing methods. Results from this analysis
are presented in Fig. 12(b) (Bars chart), considering a C.Actv of
100% and 50 US$/tonne for biomass price. As expected, the varia-
tion of capital costs implies a significant reduction of the unitary
fuel costs, being as low as 9.33 $/GJ, which is an interesting value
for further analysis and system improvements.
6. Conclusions
A comprehensive simulation and economic evaluation of
Methanol and SNG systems based on biomass gasification were
developed. Case studies were supported on real economic data
from the wood market in Chile and therefore it is a good approxi-
mation to analyze future scenarios. The modeling showed that the
gasifier operation between 800–850 °C and 0.25 equivalence ratios,
allows using the synthesis gas as energy carrier and/or as platform
for Methanol and SNG production. Energy efficiency of gasifier was
74%, and overall yields to Methanol and SNG were 0.59 kgMeOH/
kgDry-biomass and 0.33 kgSNG/kgDry-biomass respectively. These values
of yield are in good agreement with previous reports and depen-
dent of the process topology and energy management in the sys-
tem. Results suggested that working under minimum energy
requirements (determined by PINCH analysis) allows reducing
the product cost without restricting the process topology. The uni-
tary product cost (energy-based) for the integrated plant ranges
between commercial values for natural gas and Methanol. More-
over, if the potential reduction of external costs for both biofuels
is considered, their competitiveness with respect to its fossil-
based analogues can be further improved.
Acknowledgements
This work has been financially supported by the Basal CONICYT
PFB-27 (U.D.T.), FONDECYT 114041 (R.J.), PAI-CONICYT 79130023
(A.K.), FONDECYT 11140635 (A.K.) and RED Doctoral REDOC.CTA,
MINEDUC project UCO 1202 at Universidad de Concepción, Chile.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2015.11.005.
677
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