Energy 199 (2020) 117405

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Energy
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Thermodynamic analysis of methanol synthesis combining straw

gasification and electrolysis via the low temperature circulating fluid
bed gasifier and a char bed gas cleaning unit
Giacomo Butera a, *, Rasmus Østergaard Gadsbøll b, Giulia Ravenni c, Jesper Ahrenfeldt c,
Ulrik Birk Henriksen c, Lasse Røngaard Clausen a
a
DTU Mechanical Engineering, Technical University of Denmark, Lyngby, 2800, Denmark
b
Department of Energy Conversion and Storage, Technical University of Denmark, Roskilde, 4000, Denmark
c
Department of Chemical and Biochemical Engineering, Technical University of Denmark, Roskilde, 4000, Denmark

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

Article history: The phase-out of fossil fuels in the heavy transportation sector will require energy-dense biofuels like
Received 28 November 2019 methanol, and will likely require that a wide range of biomasses are utilized. In this framework, gasi-
Received in revised form fication of straw and subsequent upgrading to methanol represents a potentially advantageous con-
31 January 2020
version route. In this study, the established low-temperature circulating fluid bed (LTCFB) gasifier is
Accepted 15 March 2020
Available online 18 March 2020
coupled to a partial oxidation (POX) and char bed reactor, which enables a relatively robust and effective
conversion of tars - making the product gas suitable for methanol synthesis. Five scenarios producing
methanol via traditional air-separation units and electrolysis were thermodynamically modeled and
Keywords:
Gasification
analyzed in Aspen Plus. The analysis showed state-of-the-art biomass-to-methanol energy efficiencies up
Methanol to 54e56% and overall carbon conversions above 57%. A parametric analysis on the POX temperature
Thermodynamic analysis revealed the potential to increase efficiency and the carbon conversion up to 58% and 68%, respectively.
Solid oxide electrolysis cells The proposed systems outperform alternative systems framed on straw gasification, and exceed in terms
Straw of efficiency and overall carbon conversion other solutions based on wood-gasification.
Electro-fuels © 2020 Elsevier Ltd. All rights reserved.

1. Introduction of the key resources globally available is straw from agricultural

operations. And while this resource is applied to some extent in the
It is necessary to convert the current energy infrastructure in current energy system, it is typically regarded as a highly prob-
order to minimize the effect of global warming and secure long- lematic and notoriously difficult resource in combustion and gasi-
term sustainability. While the electricity and heating sectors are fication systems due to its ash characteristics [3]. Systems such as
being transformed by increasingly competitive wind, solar and heat the Low-temperature circulating fluid bed (LTCFB) gasifier are
pump technologies [1], the transport sector represents a major however able to convert straw effectively e see Section 1.1 for de-
challenge [2]. This is especially true for the heavy transport (trucks, tails on the system.
planes, ships etc.) that likely will require biomass-based fuels such While there are several studies on methanol production based
as methanol. Methanol has gained increasing interest in the last on wood gasification and electrolysis (e.g. Ref. [4e10]), and a lot of
decade as a viable fuel due to its combustion properties, energy laboratory investigations on straw conversion [11e14],1 only a few
density, flexible production pathways and existing global infra- studies have been found that deals with straw-to-methanol sys-
structure. Especially methanol from thermal gasification is of in- tems in a system perspective e and even fewer featuring its inte-
terest, as it represents the most energy efficient and flexible gration with electrolysis. Zhang et al. [15] and Xiao et al. [16] both
production pathway e features that are essential characteristics studied the potential of the same rice straw gasification-to-
when utilizing a heterogeneous and limited biomass resource. One methanol concept in 2009 using thermodynamic modeling e

1
* Corresponding author. Stoholm et al. proposed the concept [11] and presented results from several
E-mail address: [email protected] (G. Butera). experimental campaigns on Danish wheat straw [11e14] and manure [14].

https://doi.org/10.1016/j.energy.2020.117405
0360-5442/© 2020 Elsevier Ltd. All rights reserved.
2 G. Butera et al. / Energy 199 (2020) 117405

Nomenclature hmech Mechanical Efficiency []

hCG Cold Gas Efficiency []

Symbols Abbreviations
ASOC SOC Active Area [m2] AGR Acid Gas Removal
ASR Area Specific Resistance [U∙cm2] ASU Air Separation Unit
Cp Specific heat capacity [kJ/kg K] CFB Circulating Fluid Bed
ENernst Nernst potential [V] CHP Combined Heat and Power
HHV Higher Heating Value [kJ/kg] DC Distillation Column
iSOC Current Density SOC [A/cm2] DME Dimethyl Ether
LHV Lower Heating Value [kJ/kg] FICFB Fast internally circulating fluid bed
m_ Mass Flow Rate [kg/s] FT Fischer-Tropsch
p Pressure [bar] GDC Gadolinum doped Ceria
pi Partial pressure i-species [bar] DME Dimethyl Ether
Q_ Heat flow rate [MW] DTU Technical University of Denmark
T Temperature [
C] HT High Temperature
UF Utilization factor [] LTBIG Low tar biomass integrated gasification
VSRU;SOC Operating voltage SRU SOC [V] LTCFB Low temperature circulating fluid bed
_ MEA Monoethanolamine
W Electric Power [MW]
MeOH Methanol
xi Molar fraction i-species []
POX Partial Oxidation
yi Mass fraction i-species []
SOEC Solid Oxide Electrolysis Cell
Х Conversion []
SRU Single Repeating Unit
Dp Pressure difference [bar]
TC Topping Column
DT Temperature difference [
C]
WGS Water gas shift
h Efficiency []
his Isentropic Efficiency []

while a system concept was presented based on allothermal gasi- The LTCFB process is a staged fluid bed system that utilizes
fication, no specifically designed experimental system was pre- relatively low temperatures in order to convert typically difficult
sented. These studies investigated a coupled fluid bed system feedstocks without bed agglomeration. The gasifier is shown in
featuring steam gasification in one reactor and a combustion Fig. 1. Fuel is added to the air-blown turbulent pyrolysis reactor in
chamber in another with catalytic bed material circulating between which it is heated to 500e600
C and converted into char and gas.
them. Xiao et al. reported a cold gas efficiency of 69.5% and a The products and bed material are then carried out at the top of the
biomass-to-methanol efficiency of 42.7% for the system. Haro et al. reactor and the main solids are separated in the primary cyclone.
[17] made a modeling study in 2013 within the bioliq® concept, The solids are led to the air-blown bubbling char reactor that
which features decentralized pyrolysis and subsequent entrained converts most of the char at maximum 730
C to ensure that the
flow gasification of the oil and char fractions. Here it was shown bed does not agglomerate. The char conversion is in the range of
that the conversion efficiency of straw to syngas (overall cold gas 90% [14,20e23]. A small amount of water or steam is added to
efficiency) was 67%, a relatively low number that originates from improve char conversion and control the temperature of the char
the high-temperature entrained flow process and the stepwise reactor. The hot bed material and gas are then circulated to the
conversion of the fuel on different sites. The products of the process pyrolysis reactor. The product gas is led through a secondary
were gasoline and olefins via dimethyl ether (DME). Nakagawa cyclone and a candle filter to remove ash and particles.
et al. [18] studied in 2013 an oxygen-blown entrained flow gasifi- The key drawback of the system is the tar concentration in the
cation process with a non-defined methanol concept using various product gas, which is in the range of 30 g/Nm3 [23]. This poses a
biomasses including rice straw in experimental campaigns and challenge for the application of the gas, but recent studies have
modeling studies. The efficiency of the system was based on the investigated the use of partial oxidation (POX) and a hot char bed in
product gas composition and overall considerations. However the order to clean the gas e reducing the concentration to below 1 g/
study severely lacks transparency to allow accurate evaluation. The Nm3 [24]. Previous studies on a related system (Low-Tar Biomass
overall efficiency was estimated to 44% (biomass-to-methanol) Integrated gasification (LTBIG)) have shown that standard active
with a cold gas efficiency of 75%. carbon filters can remove such concentrations effectively [25]. Be-
ing able to clean the gas enables a series of applications including
fuel synthesis. However, in order to effectively synthesize fuels, the
1.1. The LTCFB gasifier gas should also be free of N2 [26] and hence the entire process
needs to be oxygen-blown. Experimental campaigns have recently
The LTCFB is a state-of-the-art gasifier that has been developed been carried out successfully using an O2/CO2 mixture for the
and commercialized by Danish Fluid Bed Technology, in coopera- gasifier and the POX (results to be published).
tion with the Technical University of Denmark and Ørsted, and it
has been built up to 6 MW [19]. It is characterized by its ability to
gasify a wide range of residues, including straw, sludge and manure
[20e22], into a combustible product gas at a relatively high effi-
ciency. The cold gas efficiency (including tar) is in the range of
74e79% on various feedstocks [14,22,23]. 3
Normalized with respect to the case CO2-SOEC with POX temperature of 850
C.
 G. Butera et al. / Energy 199 (2020) 117405 3

Fig. 1. Process diagram of the LTCFB gasifier [21].

1.2. Aim and char (1st cyclone) and particles and ash (2nd cyclone). A zero-
dimensional approach was used. The complex one-dimensional
This study presents thermodynamic modeling and analysis of model of a fast internally circulating fluid bed (FICFB) described
methanol production via straw gasification. The basis of the study is by Kaushal et al. [29] shows that most of the gasification reactions
the LTCFB gasifier, a gas cleaning step consisting of a POX and a take place at the bottom of the reactor, with little change in syngas
wood char bed [27], and solid oxide electrolysis cells (SOEC). Pre- composition in the freeboard, proving that zero-dimensional
vious literature showed limited interest in full-system analysis for models are sufficient [30]. The pyrolysis unit was developed as
methanol synthesis via thermochemical conversion of straw. The described in Ref. [4], applying the conservation of lower heating
novelty of the present study is the investigation of full-system high value (LHV) [31,32] and the atomic mass balance. The char gasifier
efficiency straw-to-methanol thermochemical conversion, pre- was modeled as an equilibrium reactor in accordance with [4]. The
senting novel and efficient solutions built upon different configu- recirculation of the sandy bed material from the char gasifier to the
rations. This work shows the potential of using a waste resource as pyrolysis reactor was simplified with a heat flow [30] that matches
straw, compares the proposed solutions with wood-to-methanol the pyrolysis energy requirements e details on the recirculation
conversion routes, and aims to highlight the appeal of straw for and solid concentrations can be found in Ref. [3]. Tars represented a
the synthesis of biofuels in the future transportation scenario. The large share of the LHV of the product gas from the LTCFB gasifier
study presents a comparative study of the LTCFB with air, O2/CO2 (~30 g/Nm3 on dry gas [23]). To simplify the complex mixture of tar
and O2/H2O as gasification media and showcases efficient produc- species [21], benzene (C6H6) was used as model-tar in the product
tion routes for methanol from secondary biomass resources and gas. A more thorough description of tar species was not necessary,
electricity. The oxygen is produced with either an air separation as most of the tars are cracked in the POX and char bed units. POX
unit (ASU) or SOEC. Initially, a modeling verification study of the also converts most of the light hydrocarbons in the product gas:
LTCFB gasifier is made, followed by 5 cases of different gasification these were neglected in the modeling, and CH4 was used to
media and a parametric study that investigates potentials of represent all light hydrocarbons. Table 1 shows the modeling as-
different operating conditions for the entire system. sumptions for the LTCFB gasifier. The LTCFB gasifier constitutes the
Fig. 2 represents a superstructure that describes the five state- core of the modeled state-of-the-art systems evaluated within this
of-the-art systems converting straw feedstock into methanol. work. For this reason, it was paramount to validate the model of the
LTCFB against experimental data available in the literature
2. Methods [14,20e23]. Before modeling the five case studies, a model of the
single air-blown LTCFB was created and validated. Afterwards, the
Aspen Plus from Aspentech® [28] was used to carry out the use of oxygen was investigated by mixing it with either carbon
thermodynamic modeling of the state-of-the-art systems. Redlich- dioxide or steam, similar to Ref. [26], with the aim of achieving
Kwong-Soave (RK-SOAVE) equation of states (EOS) were used for operating conditions similar to that of air.
the solid processing, Peng-Robinson EOS with Boston-Mathias
modifications (PR-BM) for gas conditioning and gas compression, 2.2. Modeling of the SOEC
and Schwartzentruber-Renon (SR-POLAR) EOS for the methanol
synthesis loop and the distillation section [4,5]. The main compo- The modeling of the SOEC is thoroughly described in Ref. [33,34]
nents, i.e. the LTCFB gasifier, the SOEC and the POX and char bed and will not be treated further. The model was updated to operate
units, are described below. All the other components were modeled with no sweep gas on the anode side. This would produce a stream
as in Ref. [5], using the assumptions shown in Table 1. The five cases of pure oxygen to be used for the O2/CO2 or O2/H2O mixtures.
are described in section 2.3.
2.3. Modeling of the POX and char bed units
2.1. Modeling of the LTCFB gasifier
POX and char bed units were modeled as a single reactor with
The modeled LTCFB gasifier consisted of a pyrolysis unit, a char WGS at equilibrium at 850
C [35], which represented the POX
gasifier and two cyclones to separate product gas from bed material temperature. However, the outlet temperature of the char bed was
4 G. Butera et al. / Energy 199 (2020) 117405

Fig. 2. Superstructure describing the five scenarios investigated within this work, for the conversion of straw to methanol via the LTCFB gasifier.

set at 800
C to estimate a temperature drop due to the conversion used as gasifying agent in the char gasifier, additional steam was
of tars. Ravenni carried out an experimental campaign on the up- not needed for the gasification reactions. When O2/CO2 mixtures
grade of pyrolysis gas from the LTCFB using a combine POX and char were used (cases CO2-WGS and CO2-SOEC), part of the CO2 from the
bed unit, observing a net consumption of char taking place from a acid gas removal was recirculated back to be used for the gasifying
POX temperature of 850
C with an excess air ratio of 0.5 in the POX mixtures. All the relevant information characterizing each one of
[24]. On the other hand, when the excess air ratio was lowered to the five cases are summarized in Table 2.
0.2, the consumption of char was negligible. For the purpose of this
work, it was assumed that the mass of char remains constant in the 2.5. Parametric analyses
bed.
Beyond the modeling and analysis of the five cases, two para-
2.4. The five cases metric analyses were carried out to investigate the effects of (1) the
POX temperature and (2) the volumetric CO2 fraction in an O2/CO2
As mentioned in the introduction, five cases were modeled and mixture. These analyses were based on the scenario CO2-SOEC.
analyzed, changing the gasification medium in the LTCFB gasifier The scope of the parametric analysis on the POX temperature
and in the POX, as well as using either a high temperature- (HT-) was to assess the improved overall carbon conversion (i.e. con-
water gas shift (WGS) or addition of electrolytic H2 as the method version of carbon from straw to methanol) at increasing POX
used to adjust the H2/CO ratio. The first case (AIR-WGS) is the temperatures. The conversion of CH4 and tars during the POX is
simplest, i.e. it is based on an air-blown LTCFB gasifier and air- higher at higher POX temperature [3], and the WGS reaction is
blown POX. WGS on cleaned product gas was used to adjust the shifted towards CO. This means that more carbon is in the form of
H2/CO ratio to a value of 2. Due to the large presence of N2, a high CO and free to react with H2 to produce MeOH. The POX was varied
methanol yield was not expected. Cases CO2-WGS and H2O-WGS from 850 to 1100
C, keeping the outlet temperature from the char
respectively used mixtures of O2/CO2 and O2/H2O as gasifying and bed 50
C below.
oxidizing agents, to improve the methanol yield by not injecting Equation (1) from Ref. [3] described the dry molar content
inert nitrogen. Case CO2-SOEC used instead an O2/CO2 mixture as xCH4 ;dry gas of CH4 in a pyrolysis gas from a fluid bed (indirectly
gasifying media in the gasifier, while pure O2 was used in the POX. heated) after POX steps at different temperatures T (in [
C]) over an
Steam electrolysis via an SOEC provided H2 to adjust the H2/CO interval from 900 to 1300
C. Due to lack of empirical data, this
ratio, as well as the pure oxygen for the gasification and POX. Case equation was adopted for these slightly different circumstances in
H2O-SOEC differed by using an O2/H2O mixture in the char gasifier. order to estimate the reduction of methane at various
In the scenarios where SOEC was not part of the system (i.e. cases temperatures:
Air-WGS, CO2-WGS and H2O-WGS), the oxygen for the O2/CO2 and .
O2/H2O gasifying mixtures in the char gasifier and POX was pro- xCH4 ;dry gas ¼ 0:0585,0:25,ð1300  TÞ ð1300  900Þ (1)
vided through an ASU. Furthermore, when the O2/H2O mixture was
 G. Butera et al. / Energy 199 (2020) 117405 5

Table 1
Assumptions used to create the cases investigated within the modeling study.

Biomass feed (Straw)

Moisture content: 10.6 wt% [21,22].
Composition (dry basis) [wt%]: C 45.8; O 40.9; H 6.0; N 1.5; ash 5.8a [36]. Dry biomass input 100 MWth (LHV).
Cp;dry straw [kJ/kg K] 1.35 HHVdry [kJ/kg] 18400 [36] Tbiomass;in [
C] 20

Pyrolysis reactor
Composition Char d.a.f. [wt%]: C 67.2; H 4.5; N 1.4 [36]
Tar content in dry product gases [g/Nm3]: 30. Model Tar: Benzeneb [23]
Dppyrolysis [bar] 0.15 Tvolatiles; out c [
C] 600 xH2 ;pyrolysis gas [] 0.0
Tchar; out d [
C] 647e659 yash;char [] 0.215 HHVchar [kJ/kg] 21100 [36]
Cp;char [kJ/kg K] 1.00 Q_loss[MW] 1

Char gasifier
Composition Ash [wt%]: C 40; ash 60. Thermodynamice equilibrium assumed at the outlet.
Tgas out [
C] 730 DpChar gasifier [bar] 0.15 Q_ loss [MW] 2
DpCyclones [mbar] 10 Tadditional steam [
C] 110 HHVash [kJ/kg] 13110

Gas cleaning
Dpparticlerem [mbar] 10 Dpsulfurrem f [mbar] 20

Compressors, blowers and ejector

his;compr [] 0.8 his;blower [] 0.4 hmech [] 0.95
hejector c [] 0.2 [37]

Partial Oxidation and Char Bed

Outlet gas at 800
C, assuming WGS at the equilibrium at 850
C (POX temperature) [35].
Tar content in dry gases [g/Nm3]: 0.6 [24]. Model Tar: Benzene.
TPOX out [
C] 850 [24] Tcharbed out [
C] 800 [24] xCH4 ;dry gas [] 0.024 [24]

High Temperature WGS

The WGS reactor is modeled as an adiabatic reactor [38] with WGS reaction at the equilibrium. Equilibrium temperature calculated between 360
C and 390
C. The WGS
reactor is located in parallel to the syngas flow, so that only a fraction of the syngas goes through it. This configuration enables to reach a H2/CO ratio of 2 at the inlet of
the methanol reactor.

Solid Oxide Electrolysis Cell

ASRd [U cm2] 0.35 [39] UF [] 0.80 xH2 ;fuelin [] 0.1
Tfuel;in [
C] 800 DpSOC [mbar] 30 Q_loss [MW] 0
Tfuel;out [
C] 800 TO2 ;out [
C] 800

Heat exchangers
Dpatmospheric p [bar] 0.01 Dpintermediate p [bar] 0.1 Dphigh p [bar] 0.8
DTMIN;gasgas [
C] 100 DTMIN;AGR [
C] 10 DTMIN;boiling [
C] 5
Q_ loss [MW] 0

Active Carbon
Complete tar adsorption at ambient temperature [24].

Acid Gas Removal

All water is removed from the syngas at the outlet of the AGR section.
DpAGR [mbar] 50 Treboiler [
C] 110 qreb [MJ/kgCO2captured] 3.8 [40]
xCO2 ;syngas out [] 0.012

Methanol synthesis
Boiling water reactor (isothermal) [41]. DTapproach of 15
C for both methanol reaction and WGS reaction. xH2 =xCO2 of 2 at the reactor inlet. Recirculation calculated setting
the molar flow rate at the reactor inlet double the molar flow rate processed by the compressors.
Treactor;in [
C] 230 Treactor;out [
C] 260 pin [bar] 85.0
pout [bar] 80.7

Distillation
Topping column (TC): 10 stages. Distillation column (DC): 35 stages. Feed stage positions optimized.
pTC [bar] 8.0 Tcond;TC [
C] 30 xCO2 ;bottomTC [ppm] 1
pDC [bar] 1.013 xH2 O;topDC [] 0.001 xMeOH;bottomDC [] 0.03

Burner for purge gas

Dpburner [mbar] 10 Tburner;out [
C] 1300 Q_ loss [MW] 0

High temperature heat pump

COP [] 4.5 [42]

ASU
w [kWh/Nm3oxygen] 0.35 [43]
a
Sulfur is neglected in the modeling since the content is below 0.2 wt% d.a.f [36].
b
Preliminary investigation on air-blown LTCFB using naphthalene instead of benzene as tar model showed a slight increase (~þ0.4%) in the heat needed for the pyrolysis,
namely resulting in a higher recirculation of bed material, balanced by a decrease in the amount of air (~0.2%) required for the POX. No difference was observed on the
methanol yield and on the efficiency of the plant.
c
Temperature of the volatiles only, used for the modeling. When mixed with hot gas from the gasifier, the product gas reaches a temperature between 647 and 659
C.
d
Set equal to the calculated outlet gas temperature.
e
The real operation of the char gasifier does not produce a gas at thermodynamic equilibrium. However the gas is mixed downstream with the pyrolysis gas, and a realistic
syngas composition is obtained by using the assumptions used in the pyrolysis reactor.
f
Sulfur removal was not modeled. However this exothermic process takes place at 250
C in a ZnO/CuO fixed bed [44].
6 G. Butera et al. / Energy 199 (2020) 117405

Table 2
The five cases investigated within the modeling study.

Air-WGS CO2-WGS H2O-WGS CO2-SOEC H2O-SOEC

Char gasifier
Gasifying agent Air O2/CO2a O2/H2Ob O2/CO2 O2/H2O
Additional gasifying agent H2O H2O e H2O e

Partial Oxidation
Oxidizing Agent Air O2/CO2 O2/H2O O2 O2

Method for H2/CO ¼ 2

WGS or SOEC WGS WGS WGS SOEC SOEC

Pure O2 provider
ASU or SOEC e ASU ASU SOEC SOEC
a
O2/CO2 mixture contains 30 vol% O2 and 70 vol% CO2 (see Section 3.1).
b
O2/H2O mixture contains 30 vol% O2 and 70 vol% H2O (see Section 3.1).

The methane content calculated by equation (1) is reduced by

12.5% when increasing the POX temperature by 50
C, within the
range 900e1300
C.
In addition, Ravenni showed in Ref. [24] a dry molar methane
content of 0.024 when POX occurs at 850
C, resulting in a per-
centage decrease of 39% in the methane content when the POX
temperature increases by 50
C, from 850
C to 900
C. For
simplicity, the same percentage decreases were applied also to tars.
The parametric analysis on the volumetric CO2 content aimed at
evaluating the reduction in the AGR heat- (and related make-up
MEA-) consumption at decreasing volumetric CO2 contents in the
O2/CO2 mixture injected in the char gasifier. A decrease of the CO2
content translates into a lower recycle rate of CO2 from the AGR to
the LTCFB gasifier. The CO2 to be removed with the amine-wash
would decrease, and so does the make-up MEA consumption.
However, a higher purity of oxygen into the char gasifier shifts the
WGS reaction away from CO in the LTCFB gasifier and POX, as there
is less CO2 available. This was expected to lower the methanol yield
and so the overall carbon conversion. In addition, the lower pro-
duction of CO at higher O2 purities lowers the requirement of H2
from the SOEC, as well as the SOEC consumption and active area.
This was expected to result in an overall reduction of the SOEC cost, Fig. 3. Flowsheet of the single air-blown LTCFB model without preheating.
which likely constitutes a big share of the plant’s investment cost
[37,45]. The volumetric CO2 content in the O2/CO2 mixture was Table 3
decreased from 70 vol% (corresponding to the case CO2-SOEC) to Thermodynamic data for the single air-blown LTCFB model without preheating.
Nodes refer to Fig. 3.
0 vol%. It is important however to highlight that the operation with
100 vol% oxygen represents a purely ideal case, since use of pure Node m_ [kg/s] T [
C] p [bar]
oxygen in the gasifier likely promotes agglomeration due to 1 6.55 20 e
excessive local temperatures, thus compromising its operational 2 11.79 662 1.18
stability. 3 1.58 662 e
4 0.57 730 e
5 6.82 730 1.18
3. Results 6 11.79 662 1.17
7 11.79 662 1.16
8 5.15 20 1.33
Results on the validation of the LTCFB gasifier are presented in
9 0.66 20 1.01
section 3.1, the five scenarios are shown in section 3.2 and the 10 0.66 20 1.34
parametric analyses results in section 3.3. 11 0.66 110 1.33

3.1. Validation of the LTCFB gasifier model efficiency for the models Air-WGS, CO2-WGS, H2O-WGS, CO2-SOEC
and H2O-SOEC was above the experimental range as preheated
The modeled air-blown LTCFB (Fig. 3, thermodynamic data in gasifying media were used. Fluctuating temperatures of the prod-
Table 3) showed that carbon energy loss (7% of fuel input), carbon uct gas in the range 647e662
C were obtained from the models,
conversion (92%) and cold gas efficiency (77%) lay within the matching the experimental data (~650
C). The slight fluctuations
experimental ranges (Table 4). Operation of the LTCFB with pre- arise from a combination of the effects of different gasification
heated air (case AIR-WGS) showed behavior similar to the air- media and their preheat temperatures. When using O2/H2O as
blown operation without preheating. Operations with O2/CO2 and gasification agent, additional steam was not added, which resulted
O2/H2O mixtures (using 30 vol% O2) both showed excellent align- in a lower mass flow and lower temperature of the product gas.
ment with air-blown operation, which is in line with previous in- Differences between the model and the real operation of the LTCFB
vestigations [26]. It is seen that the modeling results provides concern the product gas composition. A different composition of
sufficient accuracy of the LTCFB gasifier model. The cold gas
 G. Butera et al. / Energy 199 (2020) 117405 7

Table 4
Validation of the LTCFB gasifier models. Experimental values vs. calculated results from Aspen Plus.

LTCFB Experimental (No preheating LTCFB Model LTCFB Model Air LTCFB Model O2/CO2 (CO2- LTCFB Model O2/H2O (H2O-
air-blown operation) Validation e Air Preheat (Air-WGS) WGS and CO2-SOEC) WGS and H2O-SOEC)

Fuel HHV (d.a.f.) [MJ/kg] 19.6 19.5 19.5 19.5 19.5

Fuel moisture [wt.%] 10.6 10.6 10.6 10.6 10.6
Additional steam to 10e20 10 10 10 0
gasifier [wt%]
Air/Mixture preheat 20 20 700 700e722a 700e727a
temperature [
C]
Product gas temperature ~650 [14] 662 658 659 647
[
C]
Carbon energy lossb of fuel 3-11 [14,20e23] 7 7 7 7
input (LHV) [%]
Carbon conversionc [%] 86-95 [21] 92 92 92 92
Cold gas efficiency incl. 74-79 [21,22] 77 80 80 81
tars [%]
a
When using O2 from the SOEC, pure oxygen is at 800
C, resulting in slightly higher temperatures for the gasifying and oxidizing mixtures.
b
Defined as the energy loss in the LTCFB through the ash (LHV).
c
Defined as the solid to gas conversion in the LTCFB.

the tars, the presence of light hydrocarbons, and a different line and ASU. In this scenario, the overall carbon conversion and the
composition of H2, CO, CO2 and H2O might result from experi- efficiency reached 32.2% and 42.6%.
mental tests. However, the impact is negligible on the full-system The use of the SOEC to provide O2 and H2 (cases CO2-SOEC and
analysis. The downstream unit featuring POX and char bed gua- H2O-SOEC) increased the overall carbon conversion and thereby
rantees conversion of tars and light hydrocarbons over the active the methanol yield. When using O2/CO2 mixture (case CO2-SOEC),
sites of porous char structure, resulting in a real composition at the overall carbon conversion reached the highest value of 57.5%
WGS equilibrium for a temperature in the range of ~1100-750
C (Table 5), whereas the total efficiency reached 54.4%. When using
[35]. O2/H2O mixture (H2O-SOEC), H2O promoted the formation of H2
and hindered the formation of CO. For this reason, in case H2O-
3.2. Modeling results SOEC less carbon was in the form of CO, compared to case CO2-
SOEC. Less electrolytic H2 was required to adjust the H2/CO ratio,
Detailed flowsheets and related thermodynamic data for the and the operation of the SOEC was set by the O2-requirement for
five cases can be found in the Supplementary Material e also, case the oxidizing reactions in the char gasifier. However, excess H2 from
CO2-SOEC is shown in Fig. 4 and Table 5. Table 6 shows the results the SOEC represents a valuable product. The electricity consump-
for the five cases. In the case H2O-SOEC, the operation of the SOEC tion constituted a large share of the input to the system, mainly
was set by the O2 requirement for the gasification and the POX, covering the power required by the SOEC. Overall carbon conver-
resulting in an excess production of H2. sion and efficiency were respectively at 47.2% and 55.7%, resulting
The air-blown LTCFB gasifier (case AIR-WGS) produced a gas rich in a much larger methanol production in case CO2-SOEC. The same
in N2, thus lowering the overall efficiency (16.5%) and the overall operating conditions applied to the SOEC in both cases CO2-SOEC
carbon conversion from biomass to methanol (12.8%). The elec- and H2O-SOEC. However the required area for the SOEC in the
tricity consumption was mainly limited to the syngas compression scenario CO2-SOEC was significantly higher (~3600 m2 against
line, as neither ASU nor SOEC were used in this case. Low- ~2700 m2 for case H2O-SOEC, Table 5).
temperature heat was released from the methanol synthesis sec- Focusing on the effects of POX and char bed units, the energy
tion, making district heating an interesting option for this case. efficiency of the combined process was within the range of 95e96%,
An improvement in terms of efficiency and overall carbon resulting in a decrease in cold gas efficiency of ~3.2e3.8% (see
conversion was achieved in cases CO2-WGS and H2O-WGS, where Table 5).
the pure O2 provided by the ASU avoided a buildup of N2 in the
methanol reactor loop. When using a mixture of O2/CO2 as gasi-
3.3. Parametric analyses
fying agent (CO2-WGS), the large content of CO2 dampened the
formation of H2 in the POX. The large amount of unconverted CO2
The parametric analysis on the POX temperature showed an
was removed with amine wash in an acid gas removal (AGR) unit.
increase in terms of efficiency (from 54.4% to 58.3%) and overall
The removed CO2 was seen to be significantly larger than the CO2
carbon conversion (from 57.5% to 68.0%) with increasing POX
added to the gasifier. Electric power increased to cover the ASU and
temperatures (Fig. 5). However, also the active area of the SOEC
particularly the consumption of a high temperature heat pump
increased by ~33% from 3610 m2 to 4766 m2, when the POX tem-
required to provide heat for the AGR. The overall carbon conversion
perature increased from 850
C to 1100
C (Fig. 5), implying a much
and the efficiency increased up to 31.6% and 40.6%, respectively.
higher SOEC cost. With a POX temperature of 900
C or higher, a
The use of an O2/H2O mixture as gasifying agent (H2O-WGS)
heat pump is used2 to cover the increased heat requirement for the
promoted the formation of H2 at the outlet of the POX. The syngas
SOEC steam generator.
was richer in H2 than in case CO2-WGS and less syngas flowed in
The total amount of CO at the outlet of the char bed unit
the HT-WGS reactor converting CO to H2, thus keeping more carbon
in the form of CO to be converted to methanol and decreasing the
amount of CO2 to be removed in the AGR unit. Cooling of product 2
The heat pump delivers heat from the condenser to the reboiler of the distil-
gas downstream the char bed provided the evaporation heat to lation column. It works between a source temperature of 64
C and a sink tem-
supply steam to the gasifier. The high temperature heat pump was perature of 95
C, resulting in a Carnot COP of 11.88. Using a Carnot efficiency of 0.5,
avoided, limiting the need for electricity mainly to the compression the real COP is calculated to be 5.94.
8 G. Butera et al. / Energy 199 (2020) 117405

Fig. 4. Flowsheet of the potential plant for the case CO2-SOEC, using an O2/CO2-mixture for the LTCFB gasifier, pure O2 for the cleaning step and an SOEC to adjust the H2/CO ratio.

Table 5
Thermodynamic data for the case CO2-SOEC. Nodes refer to Fig. 4.

Node m_ [kg/s] T [
C] p [bar] Node m_ [kg/s] T [
C] p [bar] Node m_ [kg/s] T [
C] p [bar]

1 6.55 20 e 23 4.98 227 85.80 45 4.12 64 1.01

2 10.77 659 1.16 24 10.95 136 85.80 46 3.70 20 1.01
3 1.58 659 e 25 10.95 230 85.00 47 3.70 20 1.35
4 0.57 730 e 26 10.95 260 80.70 48 3.70 811 1.34
5 5.80 730 1.16 27 10.95 40 79.90 49 3.83 800 1.34
6 10.77 659 1.15 28 6.73 40 79.90 50 1.14 800 1.31
7 10.77 659 1.14 29 5.97 40 79.90 51 1.14 250 1.30
8 10.77 659 1.13 30 5.97 55 85.80 52 1.00 250 1.30
9 11.90 800 1.11 31 0.76 40 79.90 53 0.67 30 1.29
10 11.90 250 1.10 32 0.76 34 1.04 54 0.34 30 1.29
11 11.90 250 1.08 33 29.23 20 1.01 55 0.14 250 1.30
12 11.90 65 1.07 34 29.23 26 1.04 56 0.14 264 1.35
13 1.99 30 1.07 35 29.23 850 1.03 57 0.14 700 1.34
14 9.91 30 1.07 36 29.99 1300 1.02 58 2.69 800 1.31
15 9.90 30 1.06 37 29.99 132 1.01 59 0.58 800 1.31
16 5.26 30 1.01 38 4.22 40 79.90 60 0.98 800 1.31
17 4.64 30 1.01 39 4.22 43 8.10 61 3.15 30 1.01
18 4.98 30 1.01 40 4.22 64 8.00 62 3.15 53 1.32
19 4.98 228 4.51 41 0.10 30 8.00 63 3.15 700 1.31
20 4.98 30 4.41 42 4.12 128 8.00 64 4.13 722 1.31
21 4.98 228 19.61 43 4.12 64 1.01 65 1.13 800 1.13
22 4.98 30 19.51 44 0.01 95 1.01
 G. Butera et al. / Energy 199 (2020) 117405 9

Table 6
Results about Input, Output, SOEC operation and POX and char bed unit from Aspen Plus in the five cases.

Air-WGS CO2-WGS H2O-WGS CO2-SOEC H2O-SOEC

Input
Biomass [MWth] 100.0 100.0 100.0 100.0 100.0
Electricity [MWel] 10.4 10.9 7.5 50.5 38.4

Output
Methanol [MWth] 18.2 45.1 45.9 81.9 67.3
H2 [MWth] 0.0 0.0 0.0 0.0 9.7

Efficiencies
Biomass to Methanol [%] 18.2 45.1 45.9 81.9 67.3
Efficiency (MeOH)a [%] 16.5 40.6 42.6 54.4 48.6
Efficiency (MeOH and H2)b [%] 16.5 40.6 42.6 54.4 55.6
Carbon Conversionc [%] 12.8 31.6 32.2 57.5 47.2

SOEC
Area SOEC [m2] e e e 3610.3 2687.0
i SOEC [A/cm2]
SOEC SRU Voltage [V] 80.3 80.4 81.1 80.5 81.2

POX and Char bed 76.5 76.7 77.4 77.2 78.0

Inlet product gas [MW] 95.3 95.4 95.4 95.9 96.0
Outlet product gas [MW] 100.0 100.0 100.0 100.0 100.0
POX and char bed efficiency [%] 10.4 10.9 7.5 50.5 38.4
a
It is calculated as ðm_ MeOH ,LHVMeOH Þ=ðm_ dry straw ,LHVdry straw þ W_ Þ. This is to show the efficiency if only methanol e which is the final desired product e were considered.
el
b
It is calculated as ðm_ MeOH ,LHVMeOH þ m_ H2 ,LHVH2 Þ=ðm_ dry straw ,LHVdry straw þ W _ Þ. This is the total efficiency.
el
c
Defined as the biomass carbon ending up in the methanol.

Fig. 5. Effects of the POX temperature on efficiency, carbon conversion and SOEC area. Built on top of the case CO2-SOEC.

increased by ~12% with the POX temperature (Fig. 6). Raising the requirement, instead of the H2-requirement as in case CO2-SOEC,
POX temperature had a dual effect: (1) a deeper conversion of tars resulting thus in excess H2 production. Accounting for the excess H2
and light hydrocarbons and (2) an increased equilibrium temper- production for CO2 contents below 50 vol%, the total efficiency
ature for the WGS reaction. Both phenomena increased the amount increased up to 54.9%. Fig. 8 shows the variation of the normalized
of CO, which could then be converted into methanol. Fig. 6 illus- mole flow rate of CO2 injected in the LTCFB and normalized mole
trates the overall normalized3 mole flow rate of CO at different POX flow rate of CO in the product gas. Besides, it also shows the profiles
temperatures, as well as the normalized mole flow rate of CO if only of the normalized SOEC area and normalized AGR heat consump-
the effect of higher WGS equilibrium temperature were considered tion. Use of pure O2 limited the CO to 87.6% of the molar flow at
(this was calculated assuming the same CH4 and tar concentration 70 vol% CO2. The area of the SOEC decreased with decreasing CO2
as for a POX temperature of 850
C e meaning that the effect of tars volumetric fraction, and the curve followed the trend given by the
and CH4 conversion into CO was neglected). The curves show that CO2 injected. Finally, a lower injection of CO2 in the LTCFB gasifier
the two phenomena produces similar amounts of CO. meant less CO2 looping between the gasifier and the AGR unit, thus
The parametric analysis on the CO2 volumetric fraction in the lowering the CO2 to be removed and the consumption of the AGR
O2/CO2 mixture injected in the char gasifier showed a decrease in (Fig. 8).
the overall carbon conversion when using pure O2 (from 57.5% to
50.2%, Fig. 7). The efficiency dropped to a minimum (53.9%) when
4. Discussion
using a 50-50 vol% O2/CO2 mixture. In addition, at CO2 contents
below 50 vol%, the operation of the SOEC was set by the O2-
Calculation in Aspen Plus showed that systems using SOEC
10 G. Butera et al. / Energy 199 (2020) 117405

Fig. 6. Effects of the POX temperature on the normalized CO mole flow after the POX and char bed units. The yellow line shows the combined effect of tar conversion and increased
temperature for the WGS equilibrium. The pink line shows only the effect of the increased equilibrium temperature for the WGS reaction. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)

Fig. 7. Effects on the total efficiency (Biomass and electricity to methanol and hydrogen) and overall carbon conversion varying the CO2 volumetric fraction in the gasifying agent.

Fig. 8. Effects on different normalized factors varying the CO2 volumetric fraction in the gasifying agent.

(cases CO2-SOEC and H2O-SOEC) outperform the systems using effectively to synthesize the biofuel.4 It is also observed that, among
WGS (cases Air-WGS, CO2-WGS and H2O-WGS). The performance the solutions employing an HT-WGS reactor, the scenario with O2/
improvement (both in terms of overall carbon conversion and ef- H2O as gasifying and oxidizing media (H2O-WGS) showed the
ficiency) is possible due to the addition of electrolytic hydrogen,
instead of H2 production via an HT-WGS reactor. Relocating the
carbon from CO to CO2 for the production of H2 via HT-WGS de-
4
creases indeed the carbon that can be converted downstream to The reaction of CO2 and H2 to produce methanol is not effective as by-product
water formation inhibits the methanol catalyst. In practice, CO2 acts more or less as
methanol, as the carbon in the form of CO2 cannot be used
an inert, building up in the synthesis loop.
 G. Butera et al. / Energy 199 (2020) 117405 11

highest efficiency and overall carbon conversion (42.6% and 32.3% within the POX reactor. The SOEC area followed the same tendency
respectively). The larger presence of steam in the LTCFB gasifier and within the interval 40e70 vol% CO2, as less CO in the product gas
in the POX boosts the H2 production, resulting in a higher H2/CO required less H2 from the SOEC. However, at CO2 volumetric con-
ratio and less carbon to be transferred from CO to CO2 through the tents below 40 vol%, the SOEC operation is set by the oxygen-
WGS reaction. The modeling study revealed that the highest effi- requirement, which is more stable, resulting in a much flatter
ciency is achieved using an O2/H2O mixture as gasifying agent in curve for the SOEC area and cost.
the char gasifier, pure O2 for the POX and electrolytic H2 from the The scenarios employing the SOEC, particularly scenario CO2-
SOEC to adjust the H2/CO ratio (case H2O-SOEC, with 53.8% effi- SOEC, outperform alternative solutions to convert straw into
ciency, vs. 52.6% for case CO2-SOEC). Excess H2 represents indeed a methanol. As comparison, the thermodynamic analysis of rice
valuable co-product that can be sold, increasing the total efficiency straw conversion to methanol proposed by Xiao et al. achieved an
of the system. However, the overall carbon conversion is signifi- efficiency of 42.7% [16].
cantly higher in case CO2-SOEC (55.3%, against 45.5% for case H2O- When the focus broadens towards woody biomass feedstock, it
SOEC), using O2/CO2 mixture in the char gasifier. The excess CO2 is clear that the proposed LTCFB-based scenarios cannot compete in
injected in the gasifier promotes the formation of CO. Conversely to terms of efficiency and methanol yield with the best state-of-the-
the scenarios employing a WGS reactor, carbon is not shifted from art systems converting ligno-cellulosic biomasses into methanol.
CO to CO2 to produce H2, meaning that all the carbon in form of CO Butera et al. proposed an innovative integration of a TwoStage
could ideally be used to produce methanol. The higher amount of gasifier with SOC, achieving a biomass-and-electricity-to-methanol
CO in the product gas for case CO2-SOEC translates thus into a efficiency ranging from 63.7% to 70.5% and overall carbon conver-
higher methanol yield and overall carbon conversion. sions within 57.56%e92.3%, at different electricity prices [4]. Clau-
Steam electrolysis being a proven and commercialized tech- sen presented an analysis on methanol synthesis via wood
nology [46e48], the solutions employing an SOEC allow a much gasification coupling a pressurized entrained flow reactor and
higher performance, without adding evident complexities to the alkaline electrolyzer, obtaining an overall carbon conversion of 96%,
system. However, the SOEC is expected to cover a large share of the achieved by reusing the CO2 absorbed in a Rectisol process for
plant investment cost [37,45] and it is observed that the SOEC area biomass feeding to the gasifier, and a total efficiency of 62.5% [5].6
reduces by 25.8% from scenario CO2-SOEC to scenario H2O-SOEC, as However, scenarios CO2-SOEC and H2O-SOEC analyzed within this
less H2 is required. This has a relevant impact on the economy of the study are able to approach and exceed other state-of-the-art so-
plant, and a deeper economic analysis could be useful to estimate lutions both in terms of efficiency and overall carbon conversion.
whether it is better to prioritize the methanol yield or a lower in- For example, Holmgren et al. proposed a conversion route of wood
vestment cost. into methanol via an oxygen-blown pressurized CFB and electro-
A possible solution to increase even further the carbon con- lytic H2, with 51.8% efficiency and 44.3% overall carbon conversion
version is to recycle CO2 from the AGR back to the inlet of the SOEC. [6]. The high performance becomes more evident when the com-
Co-electrolysis (or separated CO2 electrolysis using a dedicated parison involves technologies not using electrolysis. Tock et al. [9]
stack [49]) enables to allocate more carbon into CO, maximizing the and Holmgren et al. [7] analyzed systems converting wood into
synthesis of methanol in the downstream reactor. methanol with efficiencies of 53.8% and 50.6%, respectively, and
It is moreover evident that an increase in POX temperature is overall carbon conversions of 33.7% and 32.5%, respectively.
beneficial for the system shown in case CO2-SOEC. Overall, it is In addition to the high efficiency and carbon conversion
observed that the higher WGS equilibrium temperature and the compared to other straw-gasification-based technologies, the most
deeper conversion of tars push towards the formation of CO, thus attractive key strength of the proposed systems is the use of a low-
improving efficiency (58.3% at 1100
C) and carbon conversion grade biomass such as straw. This has a significant impact on the
(68.0% at 1100
C). Allocating more carbon in the form of CO results economy and sustainability of biofuel production, as straw (1) is
in larger requirements for electrolytic H2 and SOEC area, thus cheaper than wood and (2) enables to exploit other agricultural
increasing heavily the investment cost for the plant. This assess- waste resources such as manure, biogas fibers, etc.
ment is however carried out assuming that the char bed remains As all the technologies involved in the presented processes are
intact, which is not the case at such high temperatures, as the proven to work stand-alone, proof-of-concept experiments
gasification reactions are significant. A high-level regeneration of (particularly for scenarios CO2-SOEC and H2O-SOEC) represent the
char is likely necessary, which adds to the complexity of the system. next step towards the commercialization of these technologies.
However, other materials not suffering the same attrition (e.g. Commercial plants reproducing the concepts treated in this
dolomite or olivine [50]) might be of interest in this case. At POX work, in case of operation in line with the forecasted performance,
temperatures above ~1000
C, the tar content after the POX might would produce methanol for diverse applications, including the
be sufficiently low to simply remove the bed. Residual tar could conversion to DME or jet-fuels [51e53] to fuel heavy diesel engines
then be captured by an active carbon filter,5 as proposed in the or airplanes. In a future scenario, where biomass-based methanol
presented plants, or by a scrubber. The tar levels would likely have replaces fossil-based methanol in leading the methanol market,
to be significantly lower than 1 g/Nm3 to reduce the management complementary straw-based methanol (and methanol from other
of the captured tar, depending on the given context of an actual low-grade biomass) should contribute to avoid misuse of a scarce
plant. Availability of fresh carbon and the disposal of the used, tar- resource as wood.
rich carbon is central e disposal could be done via high-
temperature processes such as combustion.
5. Conclusion
A strong correlation is observed between the decrease in the
volumetric CO2 fraction in the O2/CO2 gasifying mixture and the
A thermodynamic analysis was carried out, aiming to assess the
decrease in the overall carbon conversion. The reason is that a
reduced injection of CO2 in the LTCFB decreases CO formation
6
The lower efficiency and methanol yield of the solutions based on the LTCFB
gasifier proposed within this paper are ascribed to a better system design ensuring
5
Wood char at atmospheric temperature can be used in the activated carbon lower losses in case of [2] and to the higher carbon conversion due to higher
filter, thus adsorbing the residual tar and reducing the cost of this component. temperatures achieved within the entrained flow gasifier used in Ref. [3].
12 G. Butera et al. / Energy 199 (2020) 117405

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