10 1016@j Cej 2015 11 005 PDF

Chemical Engineering Journal 286 (2016) 663–678
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Chemical Engineering Journal

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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

suppression was also critical for the national Methanol market,
In the view of the shortage of fossil fuels and their derivatives, which reduced its production capacity to a minimum of 7.6% in ref-
switching from unsecure and polluting petro-based economy to erence to 2004 (61.01 PJ/y). Due to this situation, the government
bio-economy has been envisaged as the conscious way to reach has established policies for the development of new and more sus-
sustainable development standards. This statement becomes more tainable technologies [2]. In this framework, forest biomass
important for developing countries like Chile, which has experi- appears as a prospective candidate, based on its abundance,
enced a fast economic growth in the last decades, with a propor- renewability, carbon neutrality, and the possibility of conversion
tional effect on the energy demand (1.42 EJ in 2013) [1]. to higher-value-added products. Chile accounts for more than
Furthermore, the consumption of primary energy in Chile heavily 15 million hectares of native and forest plantations, the latter with
relies on imported fossil fuels, mainly oil (30%), coal (22%) and nat- an average yield of 35 m3/ha/y [3]. Main species in Chilean wood
ural gas (13%) [1]. Specifically, the natural gas supply was reduced plantations are Pinus radiata (60.9%), Eucalyptus globulus (22.4%)
from 266.25 PJ/y in 2004 to only 151.64 PJ/y in 2013, leading to a 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
⇑ Corresponding authors. Tel.: +56 (41) 266 1855; fax: +56 (41) 275 1233 (L.E.
Arteaga-Pérez). Tel.: +56 (41) 266 4762 (R. Jiménez).
Natural Gas (SNG) and Methanol are of special interest.
E-mail addresses: [email protected] (L.E. Arteaga-Pérez), [email protected] The advantages of converting biomass into SNG are the high
(R. Jiménez). 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 (0.20–0.23 kgSNG/kgDry,feedstock), respectively. No heat integration
the well-established and efficient end use technologies (e.g. com- was carried out and the effect of using an equilibrium model for
bined heat and power, power stations, domestic heating) [6,7]. Bio- gasification on the global exergetic efficiency was neglected. In
mass can be converted to SNG by using different processes [7,8]; as an earlier work, Mozaffarian and Zwart [9] studied the technical,
detailed in Kopysinsky et al. [7]. First stage is biomass gasification economic and environmental prospectives of waste/biomass to
to produce a syngas followed by a cleaning section, which involve SNG process. The calculated unit cost of SNG was sensible to the
physical and chemical treatments to eliminate tars, alkali and par- production capacity, being lower (8.7 $/GJ) for a plant of 15 PJ/y.
ticulate [5]. After that, the CO/H2 ratio of the syngas is adjusted in a The thermoeconomic performance of different scenarios for SNG
WGSR reactor. Thereafter, the gas is fed to the methanation system production from lignocellulosic biomass was analyzed by Gassner
(SNG synthesis) where carbon oxides and hydrogen are converted and Maréchal [10]. They concluded that higher energy and exergy
into CH4 and H2O. Subsequently, unconverted CO2 and moisture efficiencies (69–76% and 63–69%, respectively) can be obtained for
are removed from the ‘‘crude” SNG prior to its injection into the integrated plants [6,8]. The production cost of SNG (integrated
distribution grid (see Fig. 1). The overall efficiency of the process plant), including the depreciation, varied between 21 €/GJ and
is function of the individual contributions of gasification, cleaning 29.7 €/GJ for a plant capacity of 20 MWth,biomass whereas these
and methanation, hence the level of integration and energy man- values can be further reduced to 16.38 €/GJ for a higher plant
agement among systems is critical to achieve the desired results capacity (150 MWth,biomass).
[7]. Up to date, there are several works on the design and evalua- Biomass-based Methanol is also a good alternative to replace
tion of Biomass to SNG technologies, all of them based on different fossil fuels (e.g. gasoline in conventional spark engines), requiring
modeling approaches and for different biomass sources. Van der only moderate changes in the fuel distribution infrastructure
Meijden [8] analyzed, the overall energy efficiency and the CO2 [11]. Such opportunity was envisaged by Andersson et al. [11],
emissions of three wood gasification systems integrated to the which have recently investigated the techno-economic feasibility
SNG production, and suggested that CO2 balance can be neutral of integrating gasification-based biomass-to-Methanol production
and even negative if CO2 is stored. Net efficiency (excluding trans- in an industrial facility (pulp and paper mill). They suggested the
port) for the three systems varied between 54% and 67%. Neverthe- need of a special policy support to make bio-Methanol production
less, no details on the modeling approach were provided and the competitive; in such a case, the price can be reduced to 3.05–5
analysis did not include a heat integration study. Similarly, €/GJ. Moreover, authors found that using integration, the energy
Vitasarai et al. [6], performed the exergy evaluation of SNG produc- efficiency of the original process could increment by 7%. Similarly,
tion using three different feedstock (e.g. virgin woody, municipal Brachi et al. [12] studied the co-gasification of biomass and poly-
solid wastes (MSW) and sludge). In this study, maximum exergy meric wastes for Methanol production. The analyses were
destruction and irreversibilities were identified in the gasifier performed in a pilot-scale fluidized bed gasifier using air and steam
and methanation reactors, while higher exergy efficiencies as oxidizing media. The best results regarding syngas composition,
were found for woody biomass (53–58%) as compared to the relevant to Methanol production, were achieved for biomass,
other feedstock. The highest SNG yields were estimated for keeping the gasifier temperature above 750 °C and low equiva-
woody biomass (0.28–0.31 kgSNG/kgDry,feedstock) and sludge 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
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 els, this approach has the advantage of being more general,
lignin) according to the van Krevelen diagram [30]; except for because it is not associated to the resistances affecting the kinetics
municipal solid wastes (MSW) which are in the region of immature of gasification [29]. Therefore, a quasi-equilibrium model has been
oil or diagenesis. adopted here to study the biomass-to-syngas conversion process. A
scheme of the model is presented in Fig. 2.
4. Systems modeling For modeling purposes, the gasification process is divided into
several sub-units to simulate drying, pyrolysis, gasification and
A plant model for biomass gasification integrated to the produc- producer gas cleaning systems. As it has been reported elsewhere
tion of Methanol and SNG (Fig. 1) is developed using Aspen One [35–37], gasification is a complex process involving decomposition
v8.6 software. The gasification system is modeled considering a and oxidation reactions in solid and gas phases. The process takes
quasi-equilibrium approach and it is calibrated against experimen- place when air, oxygen, steam or water react with carbon from
tal data. Methanol plant is modeled based on the REtrol vision and feedstock structure to produce a gas stream (producer gas) con-
on the results reported by Clausen et al. [15]; while the SNG sys- taining: H2, CO, CH4, CxHy, CO2 and impurities such as tars, ammo-
tem uses the ICI/Koppers process concepts presented by Vitasari nia, sulfur, chlorine compounds and alkalis. Although this
et al. [6] and Kopysinsky et al. [7]. 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].
4.1. Gasification section. Model description
Accordingly, the following approximations were considered: (i)
steady state calculations, (ii) biomass is defined as non-
There is a growing interest in the modeling of gasification sys-
conventional solid using proximate and ultimate analysis, (iii) char
tems to assess its integration with energy and chemicals produc-
is represented as a conventional solid (graphite) with specific ther-
tion into the so-called biorefinery concept. In that sense, there
modynamic properties, (iv) thermodynamic properties in gasifica-
are reports on (i) kinetic [29], (ii) stoichiometric, (iii) non-
tion are estimated using the Redlich–Kwong–Soave (RKS) equation
stoichiometric and (iv) Quasi-equilibrium-based models
of state, (v) air is represented as 79% N2 and 21% O2 molar basis.
[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- 4.1.1. Operations models
fer resistances. The quasi-equilibrium approach allows quantifying Biomass dryer: Two Aspen blocks were used to simulate drying:
deviations from thermodynamic equilibrium providing a more a stoichiometric reactor (GS-01) and a flash separator (GS-02). The
realistic gas composition [33,34]. When compared to kinetic mod- wet feedstock (pine) enters at atmospheric conditions (298 K and
Fig. 2. PFD of gasification plant model.

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

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
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.
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- Fig. 6. Effect of gasification temperature on syngas composition (dry, N2-free basis)
during P. radiata gasification. ER = 0.30.
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, reaction R.2) [28,50,51]. This statement is evidenced by the propor-
investments and operation costs are determined using the refer- tional increment in CO molar fraction as well as by a reduction in
ence data reported in Table 5. Cost of feedstock was calculated the partial pressure of CO2. The increment of CO composition and
based on of regional market values for pinewood. the slight reduction in hydrogen concentration above 700 °C, could
0:7 be attributed to the combination of reverse WGSR (R.5) with
MIactual Actual Size
Cost ¼ Reference Cost o ð4Þ methane steam reforming [28,32]. At the studied conditions the
MIreference Reference Size
SN of producer gas was too low (0.31 < SN < 0.36). Therefore, it
Furthermore, sensitivity analyses on several parameters affecting should be increased in further conditioning stages, to fulfill the
the economic feasibility of the studied processes are included. 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
5. Results and discussion
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
The models described in preceding sections are used to study
CO). Similarly, above 700 °C, the effect of hydrogen oxidation
the effect of operational parameters on biomass gasification,
(LHVH2 = 120 MJ/kg) on the LHV is partially compensated by the
Methanol and SNG synthesis, and to perform the heat integration
formation of CO (LHVCO = 10.1 MJ/kg). On the other hand, the gasi-
of systems. Those analyses are the basis to estimate the economic
fier was characterized by a stepwise increment of the heat con-
feasibility of biomass gasification-to-SNG/Methanol production.
sumption from 1.27 MWth at 600 °C to 1.71 MWth at 900 °C, at an
Reported mass and energy balances are for a processing capacity
average rate of 1.7 kW/°C. When the gasification system is operated
of 1000 kg/h of P. radiata.
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).
5.1. Gasification
Based on the above discussed results, it can be inferred that
working between 800 and 850 °C could favor the use of gasification
The gasification section represented in Fig. 1 was studied at
gases in combustion and chemical synthesis applications
500 < T < 900 °C and 0.15 < ER < 0.5. Main outputs of the model
[12,25,32,42,53].
are:
U Syngas composition (mainly H2, CH4, COx) and Lower Heating 5.1.2. Effect of equivalence ratio
Value (LHV). The equivalence ratio is a determinant parameter for gasifica-
U Heat load for gasification. tion processes, as it influences the producer gas composition, reac-
U Stoichiometric number in crude gasification gas. tor temperature (autothermal operation) as well as the overall
process efficiency [25,32,42,53]. In this study, the ER was investi-
The ER was calculated based on the complete combustion of gated between 0.15 and 0.5 (at constant temperature). The value
pine, by deducing a hypothetic chemical equation as presented in of ER was determined using an approximated chemical formula
Arafat et al. [49]. The heat load in gasifier was calculated by consid- (C4.1H6.9O2.7N0.01) for biomass (P. radiata), using the data reported
ering the in situ conversion of tars. Tar was represented with a in Table 2.
model compound (naphthalene) and the heat of reaction was cal- The change of gas composition and its heating value as a func-
culated for the following stoichiometric equation: tion of ER is reported in Fig. 7. On one hand, the ER necessarily pro-
C10 H8 þ 12O2 $ 4H2 O þ 10CO2 DH ¼ 5100 kJ=mol ðR:12Þ 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
5.1.1. Effect of gasification temperature of H2 and CO decreased from 43% to 25% and 44.9% to 30%, respec-
The components profiles shown in Fig. 6 resulted from tively. This caused a reduction in the gas quality (LHV) to a mini-
heterogeneous decomposition, oxidation and reforming reactions mum of 1.6 MJ/kg at ER = 0.5. This influence of augmenting O2
(R.1–R.7). stoichiometry supply on the oxidation reactions can be verified
As temperature increases, char and tars are cracked into more by the proportional increment in the CO2 concentration from 8%
simple molecules, while carbon conversion is favored (Boudouard to 41%. A similar result was reported by Gómez-Baera [52], which
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
Fig. 7. Effect of equivalence ratio on syngas composition (dry, N2-free basis) during U Compressor power consumption.
P. radiata gasification. T = 850 °C.
U Number of stages, heat duties and recycle ratio for Methanol
distillation.
found an increment from 60% to 100% in char conversion by chang- 5.3.1. Effect of reactor temperature and pressure
ing ER from 0.2 to 0.3. On the other hand, the ER also affects the Temperature, pressure and R/P were used to decide the opera-
gasification temperature, under the condition of autothermal oper- tional point for further analyses. Table 6 summarizes the results
ation (heat is self-provided by in situ biomass oxidation). The for temperature and pressure.
higher the ER induced higher gasification temperatures, which Assuming that synthesis of Methanol takes place at equilibrium
favors the rate of reactions and the gas quality to a certain point. and based on the Le Châtelier’s principle, it can be inferred that
Therefore, a tradeoff is established between product quality and Methanol production is favored at low temperatures and high
gasification temperatures, mostly when reactors are operated at pressures [15,40,43]. Results in Table 6 corroborate the previous
autothermal regime. According to the above explained, a feasibility statement. In addition, Methanol molar fraction in products (previ-
region for ER is identified in this study, which is limited by gas ous to purification) varies between 78.4% and 89.1%, which is in
composition, gasifier efficiency and the stoichiometric number of well agreement with the data reported by Rongard [43] for an inte-
the producer gas. At ER < 0.2 the SN was 0.83; but carbon conver- grated gasification – Methanol plant using torrefied biomass as
sion was below 90%, making the operation in this range unfeasible. feedstock. In the same line, Abrol and Hilton [55] and Gutierrez-
Above ER = 0.3, the composition of gasification gas becomes more Ortiz [42], reported near 89% of Methanol molar concentration
similar to a combustion gas (CO2 > CO > H2) reducing its potential- for a syngas of similar composition and derived from an intermit-
ities for downstream applications (See LHV profile). Accordingly, tent biomass-gasification process running on solar energy.
the gasifier may be operated at 0.2 < ER < 0.3 to guarantee a syngas Methanol selectivity was between 0.99 and 1 for all the studied
LHV able to feed lean combustion ignition systems and an accept- cases and carbon oxides conversion was favored by equilibrium. In
able SN (>0.65) for further synthesis applications. At this condition, the case of CO2, the negative values for conversion, represent the
the cold gas efficiency varies between 69% and 74%. reverse equilibrium.
Neither temperature nor pressure in the reactor affected the
5.2. Gas conditioning number of theoretical stages in the distillation column. Neverthe-
less, heat duties in reboiler and condenser are reduced at expenses
The gas conditioning section is simulated by an ideal separator of a lower production of Methanol. At 220 °C and 50 atm Methanol
but using realistic values for pressure and temperature from production yield (0.59 kgMeOH/kgDry Biomass) and carbon conversion
Gutiérrez-Ortíz et al. [42]. The PSA is simulated to produce a (87.5%) are rather good. At higher pressures, this value is slightly
stream (S22) with 95% of CO2, and a mixture (S23) of H2, CO and increased, but operation at such a pressure levels may imply higher
other gases from gasification section. The level of CO2 purity was specific CAPEX/OPEX costs.
fixed based on the specification for transport and sequestration
of CO2. Results from this stage is implicit in the mass and energy 5.3.2. Effect of recycle/purge ratio
tables for both: Methanol synthesis and SNG loops. The recycle of a fraction of products in Methanol synthesis pro-
cess is commonly carried out to increase the carbon oxides conver-
5.3. Methanol synthesis loop 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
The feasibility of using syngas from P. radiata gasification for present paper, a broad range for R/P was chosen to study its effect
Methanol production is studied in this section. Typical operation on Methanol yield (Eq. (6)) and process economy respectively
temperatures (220 < T < 270 °C) and pressures (50 < P < 80 atm) [39,42,55,56]:
for Methanol synthesis are explored. Since the Methanol synthesis
F MeOH
is an exothermic reaction (R.8) and (R.9), the selection of the oper- Y MeOH ¼ 100 ð6Þ
FB
ating temperatures is subjected to a compromise between reaction
rate and equilibrium shift, while pressure is defined by reaction where YMeOH is the mass yield of Methanol (%), FMeOH is the mass
equilibria (favored at higher values) and power consumption in flow of Methanol (98%) produced in the distillation column (kg/h)
the compression train. Moreover, it has been reported that at high and FB is the flow of biomass fed to the gasification section (kg/h).
temperature (above 270 °C), the catalyst suffers sintering which Methanol production varied from 31.95% to 44.61%
leads to a decreases in the active surface area [54]. (0.13–0.22 kgMeOH/kg-gas) within the studied interval, which is
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 reported by Molino and Braccio [58] (80%), Li et al. [59] (94.5%
0.356 kgMeOH/kg-gas, but using syngas from steam reforming of for syngas from coal gasification) and to the DOE report for gasifi-
natural gas. cation gases applications [60].
Fig. 8 shows the proportional effect of R/P on YMeOH and on the As shown in Table 7, increasing system pressure and decreasing
cost related to the recycling systems (compressor and heat exchan- first methanator temperature, lead to a positive effect on methane
ger). When more than 80% of the recycle stream is fed into the production and on the conversion of CO in the first reactor (XCO-1R).
reactor (R/P > 5), the YMeOH starts to form a plateau, which can be Methane molar fraction (on wet basis) at the exit of the first
explained by the approach to the equilibrium for reactions R.8 methanator varied between 0.179 at 500 °C and 0.083 at 729 °C,
and R.9. Higher recycle do not further favor the process. Neverthe- which is similar to that reported in Gröbl et al. [18] for an inte-
less, at such a high R/P, the reactor size should augment to main- grated steam biomass gasification – one stage SNG system. These
tain residence time and the recycle compressor-heat exchanger results arise from the chemical equilibrium principles [6,58] and
should manage higher flows. Therefore, the operation costs of the can be quantified using a yield plot (Fig. 9); here yield is defined
recycle loop will grow. Accordingly, the feasibility boundaries for as the molar flow ratio between CH4 in the product stream (S42)
R/P should be defined by a compromise between the desired and CO in the feedstock (S41). Usually, the temperature of the first
Methanol yield and the costs associated to the recycle system. reaction step in methanation is constrained by the catalyst thermal
stability and it can vary between 600 °C and 750 °C [58]. For fur-
5.4. SNG synthesis loop 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
The effects of pressure and first reactor temperature on the SNG of heat to be removed (feasibility region in Fig. 9). Lower temper-
loop were investigated. Both variables influenced the rate of atures will limit the reaction rate, increasing the residence time
methane formation reaction and the energy balance of the system. and reactor size, while operation above 650 °C will decrease CH4
Table 7 summarizes the effect of the investigated operation vari- concentration and is prone to catalyst deactivation by coke deposi-
ables on mass and energy balances for the SNG Loop. tion and sintering [58].
The content of CH4 in the SNG (highlighted area in Table 7) pro- The global yield given as kg of SNG per kg of dry biomass fed
duced from biomass gasification, varied between 88.2% and 88.5%. into the gasifier, varied between 0.32 and 0.33, which is higher
The calculated CH4 composition of the SNG is similar to that 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.
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 Based on the trend of GCC (Fig. 10), both synthesis loops could
total power requirements in the plant (1464 kg/h of steam and be classified as heat sources, as consequence of the exothermic
104 kW). 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
5.5. Heat integration clear similitude in the energy trend for both: Gasification-
Methanol and Gasification-SNG, operating in standalone mode.
The opportunities for energy saving are evaluated by a PINCH Nevertheless, a higher availability of heat below the pinch
analysis. Energy targeting is carried out at best performance condi- (2061.04 kJ/h) is found for SNG, due to the higher exothermic
tions, simulated in the preceding sections. Streams data are gath- behavior of the reaction train as compared to the Methanol reactor.
ered from the simulation results of the PFDs described in Figs. 2, Therefore, this alternative is prone to be integrated with a cogener-
4 and 5. Table 8 summarizes the information of all the streams ation scheme (Blue lines in Fig. 10). Cooling requirements can be
included in the PINCH analysis. exploited to create a steam generation network with three levels
The minimum energy and area requirements for the integrated of pressure (HPS, MPS, LPS), aimed to feed a steam turbine
system (G-Integrated) were calculated by varying gasification sec- (104 kW net power) as shown in Fig. 5. Moreover, the products
tion capacity to guarantee the same flow of syngas to the SNG and from first stage methanator and producer gas could be used to
Methanol production plants. Main results of the targeting are pre- superheat the steam.
sented in Table 9. The information related to heat integration is The effect of such an integration is reflected on the utilities and
considerably expanded in Supplementary material (Heat Integra- total area requirements (39.1% higher than standalone MSL and
tion.xls), where details on data extraction, composite curves and 45.3% for standalone SNG). The co-produced steam for the inte-
heat exchanger network design are provided. grated plant (1964.49 kg/h), can be used to fulfill the requirements
Data in Table 9 are used to analyze the potential heat integra- for WGSR (210.61 kg/h) and, steam drying of biomass from 30% to
tion alternatives and the possibilities to generate services along 10%. On the other hand, has been demonstrated that varying oper-
with the main products. At the studied conditions, heat load for ating conditions (in the reaction systems) affects the global energy
gasification (1700 kW) is, by far, higher than any other heat targeting in a lesser degree [10]. Accordingly, the annual cost of
requirements. This heat must be supplied by a high temperature heat exchanger network is more sensible to the purchase cost than
source (direct heating) – usually through the combustion of the the operating cost, hence it should be designed based on minimum
biomass itself – or by an external heating (hot utility). area requirements.
Fig. 9. Effect of reaction temperature and pressure on first reactor yield.

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
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 cess yields by considering that reactions takes place at equilibrium
market). (ideal condition). These approximations result in lower unitary
It is worth noting that biomass market in Chile is prone to costs of products than those obtained under real conditions. In this
change, due to the growing interest in its use as fossil fuels substi- paper, the deviation from equilibrium in reaction systems (MSL
tute for heat and power production [22,63]. Consequently, the and SNG) was considered by introducing an approach to equilib-
uncertainties associated to forecasting the effect of biomass market rium coefficient, C.Actv, (Eq. (7)):
price on systems feasibility are relevant. Therefore, a wide interval
C:Actv ¼ 100 ðXr=XeÞ; Xe; Xr are the equilibrium
is used to explore this variable, namely 1–60 $/tonne. These values
were selected based on real market prices reported by INFOR [21]; real conversion; respectively: ð7Þ
being the lower limit the price of wood residues (sawdust) com- The impact of this coefficient on mass and energy balances as
mercialized by sawmills. Another important problem associated well as on products yield is evidenced in products cost (Fig. 12(a
to the uncertainties in economic evaluation of processes in early and b)). C.Actv. values were varied between two extremes:
stage of development is closely related to thermodynamics-based Maximum attainable yield (C.Actv = 100%): This is reached at
simulations. These calculations leads to an overestimation of pro- equilibrium conditions.
Fig. 12. Effect of biomass price and catalytic activity on the unitary energy cost.
Minimum yield (C.Actv = 10%): Assuming that catalysts are References

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Chemical Engineering Journal 286 (2016) 663–678

Contents lists available at ScienceDirect

Chemical Engineering Journal

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

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

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

A area (m2) GHG Green House Gases

Material Ultimate analysis Proximate

Fig. 2. PFD of gasification plant model.

S þ H2 $ H2 S DH ¼ 20:6 kJ=mol ðR:7Þ 4.2. Methanol plant. Models description

Fig. 4. PFD of Methanol synthesis loop.

Fig. 5. PFD of the SNG synthesis loop.

respectively. Thereafter, the temperature-enthalpy profiles

4.5. Economic evaluation

Simulation results of Gasification-SNG, Gasification-Methanol and

The effect of recycle/purge fraction (R/P) on Methanol synthesis

U Syngas composition (stoichiometric number).

Temperature (°C) Pressure (atm)

Fig. 9. Effect of reaction temperature and pressure on first reactor yield.

Processes conditions? Gasifier Methanol synthesis Methanation

Table 9 5.6. Economic evaluation

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

Minimum yield (C.Actv = 10%): Assuming that catalysts are References

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