Renewable Energy 158 (2020) 598e611

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Modelling of methanol production via combined gasification and

power to fuel
Efthymia Ioanna Koytsoumpa a, b, *, Sotirios Karellas b, Emmanouil Kakaras a, b
a
Mitsubishi Hitachi Power Systems Europe GmbH, Schifferstraße 80, Duisburg, 47059, Germany
b
National Technical University of Athens, Laboratory of Steam Boilers and Thermal Plants, 9 Heroon Polytechniou, Zografos, 15780, Athens, Greece

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

Article history: Methanol can play a significant role as a new energy carrier and can be used directly in the transportation
Received 14 January 2020 and chemical sector as well as for heat and power applications. In the present work methanol production
Received in revised form is investigated via modelling of 4 different processes combining steam-oxygen biomass gasification
14 April 2020
process and water electrolysis system as a means for energy storage. The main target is the reduction and
Accepted 30 May 2020
Available online 5 June 2020
use of direct biogenic CO2 emissions during production process and the enhancement of methanol
production capacity. This is achieved via the introduction of hydrogen from the electrolysis system, the
removal of water gas shift catalytic system, the reduction or elimination of the acid gas removal tech-
Keywords:
Methanol
nology, which result in an increase of the overall efficiency. The efficiency for the combined gasification
Gasification and power to methanol plant for the cases studied ranged between 42.82% and 52.78% without heat
CCU utilisation. The utilisation of the highly energetic off gases from the process and optimum heat inte-
Power to methanol gration were further investigated. The results showed that the total energy conversion efficiency can
Energy storage reach up to 59%. A comparison of SNG and methanol production via the combined technologies is also
Electrolysers presented, indicating that SNG production can achieve higher efficiencies.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction
Renewable Energy Directive II (REDII) includes binding targets
for member states for 32% for renewable energy consumption by
2030 and a minimum of 14% for renewables in the transport sector
by 2030 to be implemented in their national action plans. The
targets for transport were introduced to the revised directive
together with series of sustainability and Greenhouse gas (GHG)
emission criteria, the default values of which can be subject to re-
visions in the coming decade [1]. Table 1 presents the current
greenhouse gas savings thresholds as defined in RED II. Except from
the use of bioenergy and biofuels in transport, fuels of non bio-
logical origin are included recognising the electricity based fuels as
well as the recycled carbon fuels under the concept of Carbon
Capture and Utilisation (CCU). Non biological origin fuels are also
categorised currently in renewable liquid and gaseous transport
fuels of non-biological origin (ReFuNoBio) and recycled carbon
fuels (RCF), both having a threshold of 70% GHG reduction but do
* Corresponding author. Mitsubishi Hitachi Power Systems Europe GmbH,
Schifferstraße 80, 47059, Duisburg, Germany.
E-mail address: e_koytsoumpa@eu.mhps.com (E.I. Koytsoumpa).
not differentiate the bio or fossil based carbon source. As there is no
clear position if the fossil carbon sources will fall under the Euro-
pean Emission Trading System (ETS) or they will need to surrender
allowances for CCU fuels [2], biomass carbon sources can be used
for CCU fuel production without accounting for ETS carbon prices.
The use of these renewable fuels could be also extended for the
decarbonisation of heat and power sector contributing not only to
EU target in transport but also to global decarbonisation target for
at least 40% GHG reduction compared to 1990 levels towards 2030
[1] and the net-zero greenhouse gas emissions roadmap towards
2050 as envisaged by the new EU Green Deal [3]. The major
contribution of the electricity based fuels to the European energy
system is also highlighted in Ref. [4], showing the potential cross
sectoral use of thousands of TWh renewable electricity in the
harder-to-abate transport sector.
The present work presents a concept for a biomass based inte-
grated and cross sectoral industry system between power, heat and
fuel sector. Water electrolysers allow the conversion of otherwise
curtailed power to hydrogen, which is combined with syngas
produced from biomass gasification towards fuel production. In
previous published work [5], the process chain was presented for
the catalytic synthesis of Substitute Natural Gas (SNG), while in this

https://doi.org/10.1016/j.renene.2020.05.169
0960-1481/© 2020 Elsevier Ltd. All rights reserved.
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611
Table 1
Current thresholds of renewable transport fuels as defined in RED II and published in Ref. [1].
GHD thresholds in RED II
Plant operation start date Transport biofuels
Before October 2015 50%
After October 2015 60%
After January 2021 65%
After January 2026 65%
work methanol production is assessed via the combined gasifica-
tion process and power to methanol technology. A common basis
both on the methodology as well as biomass feedstock input and
gasification process has been used, while the same key perfor-
mance indicators allow the comparison of the two fuels. The
combined system allows the optimum utilisation of hydrogen and
oxygen produced in the electrolysis system, which results in the
replacement of both commonly used Water Gas Shift (WGS) and Air
Separation Unit (ASU) as well as in the partial or complete substi-
tution of the acid gas removal technology. Methanol production is
conventionally based on fossil fuels, mainly on natural gas
reforming. While in the chemical sector, it is used for the produc-
tion of formaldehyde, methyl tertiary butyl ether (MTBE) and acetic
acid and other chemicals, it can be used also in transport either in
the fuel segment such as dimethyl ether (DME), biodiesel and direct
blending into gasoline or directly as fuel [6e9].
2. Reference cases of the combined system
The general combined gasification and electrolysis system is
shown in block flow scheme for the methanol synthesis in Fig. 1,
where every technology block and its input and output mass and
energy streams have a unique numbering. Biomass is inserted in
the gasification process together with the agent, which in the
present case a mixture of steam and oxygen was used (Block 7). The
produced syngas (stream 7.2) is filtered from solid particles, such as
fly ash and unconverted biomass and cooled (Block 8) before
entering a subsequent gas cleaning and cooling process (Block 8). In
the reference cases studied, Blocks 9, 10, 2 and 3, namely the Water
Fig. 1. General block flow diagram for methanol production via the combined concept.
599
Transport renewable fuels of non-biological origin Electricity, heating and cooling
e e
e e
70% 70%
70% 80%
Gas Shift (WGS) process and medium temperature cooling (Block
9), the conditioning unit and bulk sulphur species removal with
activated carbon, indicated as “S removal (Block 10), the Acid Gas
Removal (AGR) (Block 2) and the scavenging process before
compression (Block 3) process have different specifications as
presented in Table 2. The energy input in Block 7 remains the same
for cases denoted as B1 and denoted for cases B2. Depending on the
gasification parameters, on the fuel used but mostly on the gasifi-
cation agent, steam or oxygen or a mixture of those influence the
syngas composition and the ratio of hydrogen to carbon monoxide
and carbon dioxide. In the present work, steam oxygen gasification
has been used, which as explained in the following paragraphs did
not require the use of water gas shift reaction for moderating
higher hydrogen content and stoichiometric number for the sub-
sequent methanol process (indicated as strikethrough WGS in
Table 2).
A simplified process diagram summarising the different cases
studied is presented in Fig. 2. AGR process is depicted in doted lines
as the process was used in basic scenarios B1a and B2a, but it was
not required in the cases B1b and B2b. In cases B1a and B2a, the
electrolyser system was sized according to the oxygen demand,
while in cases B1b and B2b the electrolyser system was oversized
allowing the elimination of AGR process and the maximum uti-
lisation of the carbon contained in the biomass fuel.
In cases B1a and B2a, the AGR process with Methyldiethanol-
amine (MDEA) as solvent, while in the scavenging process activated
carbon (AC) was considered. As mentioned above, the main dif-
ferences between the studied cases are the AGR and electrolyser
system leading to different methanol production sizes. Thus, in
600 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

Table 2
Modelling cases for Methanol synthesis.

Methanol Units per case

Gasifier Filtration/ Condi-tioning WGS Conditioning AGR Conditioning

Conditioning

7 8 8 9 10 2 3

B1a Steam/O2 800  C/5 bar sunflower Cooling HT Filtration Tar removal (Olga) WGS/Cooling S Removal/ MDEA Scavenging with AC/
Cooling MT 400  C MT Condensation Compression
40  C
B2a Steam/O2 1000  C/20 bar sunflower Cooling HT Filtration Tar removal (Olga) WGS/Cooling S Removal MDEA Scavenging with AC/
Cooling MT 400  C MT Condensation Compression
40  C
B1b B1a þ PtF Cooling HT Filtration Tar removal (Olga) WGS/Cooling S Removal e Scavenging with AC/
Cooling MT 400  C MT Condensation Compression
40  C
B2b B2a þ PtF Cooling HT Filtration Tar removal (Olga) WGS/Cooling S Removal e Scavenging with AC/
Cooling MT 400  C MT Condensation Compression
40  C

*MT: Medium Temperature, HT: High Temperature.

Fig. 2. Simplified process flow diagram for methanol production via the combined process.

terms of process scheme Block 3, 4 and 5, namely the compression,

the methanol synthesis and the distillation have no differences.
However the syngas composition, mass and energy balances are LHVfuel;out: ,mfuel;out
CFEF ¼ (1)
different as presented below. LHVreactant: ,mreactant

The cold fuel efficiency for the combined process based on the
biomass energy input in LHV and the total electricity input.

2.1. Key performance indicators

LHVMeOH;out: ,mMeOH;out
CFEG&PtMeOH ¼ (2)
As also presented in Refs. [5], three key performance indicators LHVfuel; in: ,mfuel; in þ Ee;in
were defined for the comparison of the different cases.

The cold fuel efficiency or chemical fuel efficiency (CFEF) based
The energy conversion efficiency (ECE) as the overall efficiency
on Lower Heating Value (LHV): of the integrated system including the thermo-chemical energy
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 601

output and the total energy input in terms of thermal energy
and power.
LHVMeOH;out: ,mMeOH;out ±Eout
ECEG&PtMeOH ¼
Ein ±Total Electric Powerin
2.2. Main process blocks and modelling results for the syngas fed to
methanol synthesis
For all modelling cases, sunflower was used as gasification
feedstock. The fuel is based on second generation biomass as it is
based on sunflower cake after oil extraction, which was treated and
delivered in the form of pellets. The fuel analysis as well as the
results of gasification modelling were published in Ref. [5] and are
here given in Table 3 only as an overview of the further process
calculations for the small scale gasification with thermal fuel input
of 20.05 MWth and operating parameters at 5 bar and 800  C (Case
1) and for the larger scale gasification with thermal fuel input of
81.17 MWth and operating parameters at 1000  C and 20 bar (Case
2). The use of the steam and oxygen mixture in the gasification
process allowed the elimination of water gas shift process, which is
a prerequisite in oxygen based gasification without any addition of
hydrogen from other sources. In the case of methanol production a
stoichiometric number equal to 2 is required, which in the studied
cases is achieved with the addition of hydrogen from electrolysers
in all cases and the removal of carbon dioxide (via AGR) in cases
denoted with an a, B1a and B2a. The CFEF is equal to 80.86% and
77.97% for Case 1 and Case 2 respectively. Finally, in Table 3 im-
purities are also presented for the two cases. These have to be
treated and removed via gas cleaning and conditioning processes.
(3)
Syngas cooling is applied in all cases and takes place after the
gasification process at the temperature of 600  C where filtration is
included and subsequent cooling syngas at 400  C (Block 8). Then,
syngas is fed at 400  C in the tar removal system, which in all cases
the OLGA™ tar separation technology with multi-stage oil scrub-
bers was considered [10,11]. Impurities after gasification include
also organic sulphur species, which might not be removed by acid
gas scrubbing and cause damage to subsequent processes. Organic
sulphur traces can be treated with activated carbon [5,12e15].
Although a number of heterocyclic sulphur compounds such as
mercaptans or thiols (for example thiophenes (C4H4S), meth-
anethiol, ethanethiol, thioethers, benzothiophenes (C8H6S),
dibenzothiophenes (C12H8S)) can be produced, in the present work
only COS and CS2 were considered [14,15], which in all cases were
treated at 230  C (Block 10). As presented in Refs. [5], further
sulphur species removal is taken place at the scavenging stage as
the presence of water content greatly enhances the adsorption of
H2S such as in activated carbon impregnated with NaOH/KOH or
K2CO3, or a similar caustic material [16,17]. As mentioned above, the
catalytic water gas shift unit is not employed here as in the case of
SNG production, where a higher stoichiometric number is required
for the synthesis [5,14]. MDEA is studied as acid gas removal (AGR)
process, which can remove in parallel hydrogen sulfide and carbon

Table 3
Steam/Oxygen gasification for sunflower at 800  C/5 bar and 1000  C/20 bar [5].

CASE 1e800  C/5 bar CASE 2e1000  C/20 bar

Stream Unit Value Stream Unit Value

7.0 Heat(Input) MWth 20.05 7.0 Heat(Input) MWth 81.17

7.1 Electricity MWe 0.116 7.1 Electricity MWe 0.468
7.2 Syngas M (kg/s) 1.771 7.2 Syngas M (kg/s) 7.649
7.3 Agent M (kg/s) 0.6985 7.3 Agent M (kg/s) 3.304
7.4 Fuel M (kg/s) 1.175 7.4 Fuel M (kg/s) 4.758
8.2 Syngas M (kg/s) 1.77 8.2 Syngas M (kg/s) 7.648
CASE 1 -Composition at 800  C and 5 bar
Mol % H2 N2 O2 H2O CO2 CO CH4
7.2/8.2 26.75 1.07 25.6 19.13 19.6 5.39
7.3 31.17 68.83
Mol % C2H4 H2S COS CS2 HCl Other Tar
7.2 2.19 0.118 0.003 <1 ppm 0.002 0.12
7.3
8.2 2.19 0.112 0.003 <1 ppm <2 ppm 0.12
CASE 1 CFEF 80.86%
CASE 2-Composition at 1000  C and 20 bar
Mol % H2 N2 O2 H2O CO2 CO CH4
7.2/8.2 27.87 0.96 27.61 14.66 25.98 1.94
7.3 61.59 38.41
Mol% C2H4 H2S COS CS2 HCl Other Tar
7.2 0.79 0.11 0.003 <1 ppm 0.002 0.05
7.3
8.2 0.79 0.10 0.003 <1 ppm <2 ppm 0.05

CASE 2-CFEF 77.97%

Proximate Analysis of Sunflower on weight dry basis and Heating Values

(% w/w) Fixed Carbon Volatiles Ash Moisture HHV* (MJ/kg) LHV (MJ/kg)

Sunflower 14.24 76.79 8.97 8.10 18.92 17.06

Ultimate Analysis of Sunflower on weight dry basis
(% w/w) C H N S O Cl
Sunflower 47.00 5.71 2.34 0.31 35.60 0.07

XRF Analysis of Sunflower on weight dry basis

(% w/w) SiO2 Al2O3 Fe2O3 CaO MgO K2O P2O5

Sunflower 6 2.3 0.4 25.3 12.9 16.1 14.8

*HHV: Higher Heating Value, nd: not defined.

602 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

dioxide for the cases B1a and B2a. However, in cases B1b and B2b,
removal for sulphur organic species at 230  C (Block 10) and after
condensation hydrogen sulfide removal is performed with acti-
vated carbon in the scavenging process (Block 3). The modelling
process of AGR in ApenPlus™ with MDEA solvent, the Electrolyte
NRTL (NRTL) model using Redlich-Kwong-Soave (RK-SOAVE) and
the reaction scheme was presented in Ref. [5]. The results of the
model are presented in Table 4.
Although the removal of hydrogen sulfide in MDEA reaches 99%,
the removal of HCl is equal to only 34.74% and 65.77% for the two
cases studied with AGR. In all cases, tar, HCl and H2S need to be
removed from the synthesis gas as they can act as poisons to the
subsequent catalytic processes [18]. The results of the main process
streams for each process block and for each case studied are pre-
sented in Table 5.
The water electrolysis (Block 1) was not modelled, but pres-
surized alkaline water electrolysis at 30 bar with a total electrical
efficiency h_electrolyser equal to 4.3 kWh/Nm3 defined at 25  C
was used [5]. For the cases B1a and B2a, the electrolysers were sized
according to the oxygen demand for the replacement of Air Sepa-
ration Unit (ASU) in the gasification process presented in Table 3
resulting in 7.375 MWe for the smaller system (Case B1a) and
41.133 MWe for the larger system (Case B2a). For the cases B1b and
B2b, the electrolysers were oversized according to the syngas
composition resulting from the elimination of AGR process and the
requirements of the methanol synthesis. According to the results
presented in Table 5 for the syngas composition remaining un-
changed for streams 10.2 and 2.2, 22.403 MWe electrolysers are
needed for the smaller system (Case B1b) and 97.820 MWe for the
larger system (Case B2b).
3. Methanol production via combined concept
In Fig. 2, the configuration of catalytic methanol production was
presented. After scavenging and removal of condensates at 40  C,
the biomass derived syngas is fed to the first compression unit,
where it is compressed at 30 bar and further cooled before mixing
with the hydrogen at 30 bar takes place. Continuously, the reactants
are mixed with the recycle stream and fed in a cross flow heat
exchanger for reaching the desired temperature in the methanol
reactor.
The methanol synthesis was modelled with equilibrium and an
RGibbs reactor in AspenPlusTM. The basis of the present
conventional production of methanol is the low pressure process
with Cu/ZnO/Al2O3 based catalysts operating between 200 and
300  C and 50e100 bar. Synthesis gas can be obtained from many
sources such as reforming of natural gas, coal or other carbon
sources, but the main set of reaction scheme remains the same as
shown in Table 6 [9,19e23]. In the present work, an adiabatic
reactor operated at 80 bar was considered. The reactor product is
fed to the cross flow heat exchanger, where the reactants are
heated, and is subsequently further cooled before entering a flash
for the separation of gaseous and liquid products. The gases are
recycled back to the reactor with the support of the recycling
compressor, while the liquid mixture mainly composed of meth-
anol and water is throttled at 3 bar and sent to the distillation unit.
The distillation unit is used to purify the crude methanol to a higher
purity grade (for example Grade AA higher than 99.9%) as its
principal is the thermal separation of mixtures to single pure
components according to their different boiling points at certain
pressure. Distillation is shown in Fig. 2 with three columns used for
the separation of light gases diluted in the liquid mixture, for the
separation of water and methanol as well as for the separation of
byproducts with similar boiling points to that of methanol (impu-
rities such as ethanol, propanol, butanol, acetol and ketones may be
formed [9,19]. The sum of purge and off gases released is initially
considered as losses, but lateron the utilisation of these streams is
assessed.
3.1. Results of methanol production via combined concept
The results for the methanol synthesis are presented in Table 7.
As it can be seen in Table 7, there is a significant amount of
unreacted gases leaving the methanol unit. The methane and
ethene content have been considered as inerts in the catalytic
methanol reactor, thus they are recycled in the methanol synthesis
unit and leaving the system at the purge stream. These gases are
losses for the whole process as mentioned before. Specifically, for
the cases B1a and B1b, the purge losses are equal to 5.5 MWth and
5.8 MWth, while for the cases B2a and B2b, the purge losses are
equal to 8.7 MWth and 9.9 MWth. These high energy content gases
should be used within the process in order to improve either the
chemical production or the heat utilisation, which is further on
discussed.
The total input and output energy streams are outlined in
Table 8. The CFEF for methanol process only as well the cold fuel

Table 4
Modelling results of AGR process for methanol synthesis- Case B1a and B2a.

CO2 Capture with MDEA

Case B1a B2a

Specification Unit MDEA MDEA

Capture ratio % 81.81 89.99

Solvents (% wt) 40 40
Mass CO2 captured kg/s 0.58 2.201

T Solvent (inlet/outlet) absorber C/ C 38/67 38/72

T Gas (inlet/outlet) absorber C/ C 40/55 40/59
Solvent/gas flow rates (L/G) kg/kg 8.75 21.18

T Solvent (inlet/outlet) desorber C/ C 86/86 86/86
Theoritical Stages of absorber/desorber 5/4 5/4
Pressure (absorber/desorber) bar 4.6/1.1 15.5/1.1
Power consumptions MWe 0.005 0.071
Specific power consumptions MJel/kgCO2cap 0.009 0.032
Reboiler Heat duties MWth 1.38 4.1
Specific reboiler duties MJth/kgCO2cap 2.38 1.863

Reboiler temperature C 105 105
H2S Removal % 99.96 99.98
HCl Removal % 34.74 65.77
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 603

Table 5
Methanol - Main Process Streams results per block and per case studied.

No Stream/Case B1a m (kg/s) B2a m (kg/s) B1b m (kg/s) B2b m (kg/s)

9.2 Syngas 1.771 7.648 1.771 7.648

9.3 Steam e e e e
10.2 Syngas 1.386 5.745 1.386 5.753
10.3 Condensates 0.374 1.879 0.374 1.871
2.2 Syngas 0.802 3.54 1.386 5.753
2.5 CO2 rich gas 0.654 2.431 e e
% Mol Composition Stream 10.2
H2 35.53 38.40 35.53 38.40
N2 1.42 1.33 1.42 1.33
H2O 1.41 0.42 1.41 0.42
CO2 25.41 20.2 25.41 20.2
CO 26.04 35.79 26.04 35.79
H2S 0.09 0.09 0.09 0.09
CH4 7.16 2.68 7.16 2.68
HCl 2ppm <2 ppm 2ppm <2 ppm
Tar 0.015 0.007 0.015 0.007
C2H4 2.92 1.09 2.92 1.09
P (bar) 4.6 16.5 4.6 16.5
T ( C) 40 40 40 40
% Mol Composition Stream 2.2
H2 44.95 47 35.53 38.40
N2 1.8 1.62 1.42 1.33
H2O 1.72 0.52 1.41 0.42
CO2 5.85 2.48 25.41 20.2
CO 32.93 43.78 26.04 35.79
H2S <1 ppm <1 ppm 0.09 0.09
CH4 9.06 3.28 7.16 2.68
HCl <2 ppm <1 ppm 2ppm <2 ppm
Tar <1 ppm <1 ppm 0.015 0.007
C2H4 3.69 1.33 2.92 1.09
P (bar) 4.4 15.4 4.6 16.5
T ( C) 40 40 40 40
Scavenging requirements
H2S e e <1 ppm <1 ppm
HCl <1 ppm <1 ppm <1 ppm <1 ppm
Tar <1 ppm <1 ppm <1 ppm <1 ppm

Table 6
The main set of methanol reactions.

Methanol Reactions:

COþ2H2 4 CH3OH DHR ¼ 90.8 kJ/mol

CO2þ3H24 CH3OH þ H2O DHR ¼ 49.6 kJ/mol
CO2 þ H2 4 CO þ H2O DHR ¼ þ41 kJ/mol

efficiency for the combined concept are also presented. Case B2b
with pressurized steam oxygen biomass gasification presents the
highest efficiency. As presented in Table 8, the cold fuel efficiency
for the combined concept of methanol production for cases B1a and
B1b, and B2a and B2b is 42.82%, and 46.77%, and 52.04% and 52.78%
respectively.
In Fig. 3 and Fig. 4, the main energy balances for the methanol
production in case B1a and B1b, as well as in case B2a and B2b are
presented. The fuel energy input and the power input expressed in
MWth/e, while in the right side the shares of the power input and
methanol output are expressed as percentages based on the
biomass energy input (100%). The black arrows shown in the dia-
grams are not energy losses of the total system but the energy,
which is not converted to methanol. A detailed analysis of the heat
streams and energy losses is presented in the next chapter for the
optimum cases. Comparing the low pressure and low temperature
gasification process (Case B1 - 5 bar/800  C) and the gasification in
higher pressure and temperature (Case B2 - 20 bar/1000  C) it is
shown that a higher electrolyser capacity is required for the latter
compared to the biomass energy input; while the methanol pro-
duction is also higher for the gasification in higher pressure and
temperature (Case B2 - 20 bar/1000  C).
The purge stream has a significantly high influence, which is
more obvious for case B1a and B1b. In the case of oversized elec-
trolysers, the purge loss has a lower effect compared to the total
energy input in all cases due to the fact that more hydrogen is
introduced and the molar content of unreacted gases is reduced.
Coal based methanol production can have significantly varying
efficiencies ranging from 38 to 55% [7,16e19]. Those values are
similar to the results presented here for a combined power to fuel
and gasification scheme with the best cases of B2a and B2b to reach
an efficiency of 52 and 52.78%. It is concluded that high tempera-
ture gasification is required to achieve higher efficiencies in
methanol production as the methane and Cþ content highly in-
fluence the subsequent process (here methane and ethene content
considered as inerts).
3.1.1. Utlisation of purge stream in methanol production
The high energy content of purge stream could be further uti-
lised towards either further production of methanol or via its use in
the gasification process or for further heat/steam production. The
use in the gasifier could be achieved either via continuous feed in
604 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

Table 7
Methanol Production - Main Process Streams per block and per case studied.

No Stream/Case B1a m (kg/s) B2a m (kg/s) B1b m (kg/s) B2b m (kg/s) P (bar) T ( C)

1.2 Hydrogen 0.042 0.232 0.126 0.552 30 30

1.3 O2 0.315 1.757 0.957 4.178 30 30
1.4 Water 0.357 1.989 1.083 4.73 atm atm
3.2 Compr. syngas 0.83 3.761 1.496 6.286 80 145
3.3 Condensates 0.013 0.011 0.013 0.008 1 40
4.2 Crude MeOH 0.689 3.465 1.343 5.941 3 45
4.3 Purge 0.142 0.296 0.153 0.345 76 43
5.2 Pure MeOH 0.61 3.273 1.027 4.846 atm atm
5.3 Gas Losses 0.025 0.081 0.023 0.086 atm atm
5.4 Condensates 0.054 0.111 0.293 1.009 atm atm
% Mol Composition Stream 3.2
H2 60.9 64.25 66.88 68.11
N2 1.31 1.09 0.74 0.68
O2 0.03 0.03 0.05 0.05
H2O 0.32 0.33 0.38 0.37
CO2 4.25 1.67 13.19 10.41
CO 23.93 29.52 13.52 18.43
CH4 6.59 2.21 3.72 1.38
C2H4 2.68 0.89 1.52 0.56
% Mol Composition Stream 4.2
H2O 13.74 5.94 33.7 27.11
CO2 0.06 0.08 0.08 0.17
CH4 0.06 0.07 0.03 0.03
CH3OH 85.84 93.6 66.08 72.58
C2H4 0.29 0.29 0.12 0.11
% Mol Composition Stream 4.3
H2 9.69 20.72 15.78 28.72
N2 11.63 20.78 10.5 17.5
H2O 0.06 0.03 0.13 0.13
CO2 1.13 1.05 2.6 4.26
CO 1.3 6.14 1.19 4.37
CH4 55.99 38.64 50.75 33.09
CH3OH 1.34 1.6 1.11 1.37
C2H4 18.87 11.03 17.93 10.55
% Mass Composition Stream 5.2
H2O 0.13 0.16 0.16 0.16
CH3OH 99.87 99.84 99.84 99.84

Table 8 where steam or electricity can be produced. This option is discussed

Methanol Production e Main energy streams per block and per case studied. in the next paragraph, where heat integration of the optimum cases
No Stream/Case B1a B2a B1b B2b is performed.
7.1 MWe 0.116 0.468 0.116 0.468
For the methanol synthesis, the respective cooling and heating
8.1 MWe e e e e demand is given in Table 9. In Fig. 5 the T-Q Diagrams are shown
9.1 MWe e e e e without considering optimum heat integration in the overall sys-
10.1 MWe e e e e tem studied per each case. As it can be seen, in all cases, a reboiler
2.1 MWe 0.005 0.07
duty is denoted. The reboiler duty or heat demand for all cases
1.1 MWe 7.375 41.133 22.403 97.820
3.1 MWe 0.63 1.693 0.909 2.443 takes into consideration the heat required for the crude methanol
4.1 MWe 0.126 0.428 0.162 0.496 distillation process and its preheating demands as well as the heat
5.1 MWe <0.001 <0.001 <0.01 <0.01 required for the acid gas capture process (only for cases a) and the
Total Stream/Case B1a B2a B1b B2b process steam required for the steam oxygen biomass gasification.
electricity MWe 8.253 43.794 23.6 101.236
fuel (solid) MWth 20.046 81.171 20.046 81.171
As it can be seen, cases B1 not only present low cold fuel effi-
MeOH MWth 12.118 65.026 20.414 96.282 ciencies but also lower potential for heat integration. In this regard,
CFEF % 57.95 72.64 66.92 76.58 no further analysis is hereby performed. On the other hand, cases
CFE G&PtF % 42.82 52.04 46.77 52.78 B2 present higher cold gas efficiencies and due to the larger scale
additional steam production is considered. In the following analysis
for the optimum cases, process steam production at 20 bar for
the gasifier, -which in the case of entrained flow gasifiers could be covering the gasification needs and medium temperature heat
optimally achieved- or via its intermediate storage and use as a (200  C) for heat industrial consumers with thermal needs in the
start up fuel. This option requires a modification of the gasification temperature range 90e180  C is considered.
agent as it influences the gasification conditions and downstream
processes and it is not further analysed here. The use in the 3.2. Heat integration for Case B2a and Case B2b
methanol synthesis process requires the installation of further
equipment such as the steam methane reforming catalysts. It has to Heat integration is achieved via utilizing the available heat from
be mentioned that steam reforming of methane necessitates a the system in order to produce steam for two purposes: the first
highly purified syngas and high temperatures due to the catalyst refers to the separate steam cycle producing steam as a gasification
poisoning and endothermic reaction. The third option is the com- agent and the second for covering the internal heat demand of the
bustion of the purge stream in a heat recovery boiler or gas turbine, two systems studied. The results are presented in Fig. 6. Compared
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 605

Fig. 3. Case B1a (top) and B1b (down): Main energy streams expressed in MWth/e (left) and as percentage of biomass energy input (right).

Fig. 4. Case B2a (top) and B2b (down): Main energy streams expressed in MWth/e (left) and as percentage of biomass energy input (right).
606 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

Table 9
Gasification and Power to methanol plant -Cooling and Heating demand.

Thermal Energy- Cooling demand (Hot streams)

Hot B1a B1b B2a B2b

MWth MWth MWth MWth

1.0 Air cooled Air cooled Air cooled Air cooled

2.0 1.908 e 7.032 e
3.0 0.413 0.511 0.535 0.590
4.0 3.060 5.069 15.525 23.136
5.0 1.369 2.572 6.868 11.656
7.0 0.708 0.708 6.033 6.033
8.0 0.668 0.668 2.820 2.820
9.0 0.529 0.529 2.277 2.277
10.0 1.479 1.479 7.016 7.016
Thermal Energy- Heating demand (Cold streams)
Hot B1a B1b B2a B2b
MWth MWth MWth MWth
2.0 2.151 e 7.502 e
5.0 1.344 2.520 6.749 11.431
7.0 1.096 1.096 4.556 4.556
Steam provision
MWth 0 0 1.498 3.123
% of MeOH e e 2.30 3.24
% of solid fuel e e 1.95 3.85

Fig. 5. T-Q Diagrams for all methanol cases: No heat integration.

to SNG cases presented in Refs. [5], heat utilisation in the methanol
cases is limited. This is due to the lower temperature level of heat
provision in the catalytic synthesis. In addition, process steam
production for cases B2 requires steam at 20 bar for the gasification,
which subsequently requires a higher temperature heat provision.
For both cases, process steam is produced with heat recovery and
additional steam for both internal and external use is produced
denoted as heat for reboiler duties and external provision. The total
amount equals to 7.987 MWth, which in case of B2a will cover the
total reboiler duties and provide the surplus of 1.498 MWth to
external consumers and in case B2b the surplus 3.123 MWth.
It is noted here that for both cases heat recovery within the
process was performed in the high temperature area of the hot
composite curve, which is basically the recovered heat from syngas
gasification (Block 7) to the medium temperature cooler of the gas
cleaning unit (Block 10) at the temperature range 1000  Ce230  C,
while the economizer of the process steam is also partly recovering
heat from lower temperature coolers in Block 2. As the gasification
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 607

without an additional steam cycle. An air compressor with 2 stages

and intercooling, which delivers the air flow of 6.7 and 7.62 kg/s for
the two cases at a pressure of 27 bar with an isentropic efficiency of
80%, a combustion chamber and a gas turbine with an isentropic
efficiency of 85%, that delivers the flue gases at a temperature of
570  C and pressure of 1.03 bar to the heat recovery boiler are
considered. The fuel (purge stream) is throttled at 27 bar and fed to
the combustion chamber. The efficiency is equal to 31.69% for case
B2a and 31.75% for case B2b, producing 2.74 and 3.14 MWe. In
addition, stream 5.3 equal to 2.75 and 2.04 MWth for case B2a and
B2b respectively is burnt in the heat recovery boiler (HRB). The total
available heat from the two streams is equal to 7.63 and 7.65 MWth
and the additional steam production is equal to 5.81 and 5.83 MWth
for case B2a and B2b respectively. The results are presented in Fig. 7
and in Table 10.
As shown by the analysis made above, there is a high amount of
steam available for industrial consumers. In case both the purge
stream and off gases were burnt in the GT, the cold fuel efficiency
could be increased to 53.59% and 53.91% for the cases B2a and B2b
respectively. In the present analysis, the steam required for the
gasification process (gasification agent) was produced with heat
recovery from the produced syngas. However, the GT-HRB could be
a more flexible option for start up operation, where the heat
recovered there would be only adequate if the off gases were burnt
in the HRB as presented above. When the process is applied in
higher scale and higher masses are treated, the efficiency of the
rotor-machinery used could lead to an improvement in the overall
process. Finally, it is noted that the electric consumptions in the
total steam production as well as in the cooling system were not
considered in the above analysis.
In all above considerations steam was considered for external
provision. However, if there are no industrial consumers, lower
temperature heat could be provided to a district heating grid. A
further optimization can be performed in Case B2b, where an
additional high amount of heat in the range of more than 5MWth is
available in temperatures above 125  C, which would increase the
total energy conversion above 60% in the above studied case.

3.3. Comparison of SNG and methanol production via the combined

system

As mentioned before, the above methodology is similar to the

work published in Ref. [5] for the SNG production. A comparison is
hereby presented between the two fuels for the combined gasifi-
cation and power to fuel process based on first on the same treated
biomass input and secondly on the same fuel production plants.
For the comparison of the two fuels, the similarities and dif-
Fig. 6. T-Q Diagrams for optimum MeOH cases, Case B2a (middle) and B2b (down)
ferences on the combined process scheme are hereby outlined:
without use of purge stream and distillation off-gases.

Gasification and Filtration/Tar Removal System Unit 7 and 8: The
exact same mass and energy balances, same fuel characteristics,
process has the exact same size for the two studied systems, the gasification process parameters and steam and oxygen mass
same amount of heat is recovered and the same amount of steam is flows, with the exact same output are modelled and presented
fed to the gasifier. However, the two process have considerable in the present work and in Ref. [5] as also shown in Table 3.
differences in the energy demand as case B2b has no AGR, but has
Water gas shift Unit 9: There is no water gas shift system in the
higher reboiler duties in the distillation due to the higher amount of methanol case produced via the combined process. In a biomass
crude methanol treated. gasification system alone, and especially in oxygen gasification,
The utilisation of purge stream is further investigated for the the water gas shift part is needed in the methanol production
two cases. The purge stream could be combusted in a heat recovery process, but in the combined system with electrolysis it can be
boiler with air or with the additional oxygen production in the case eliminated. In the same system for SNG production, the WGS
B2b with oversized electrolysers. On the other hand, it could be unit was needed for Cases A1a and A2a [5].
utilised in a combination of a gas turbine and a heat recovery boiler.
Sulphur removal in Unit 10 and Unit 3: In terms of process steps
The second option is presented here with the installation of and sequence these units are the same for both methanol and
compact open cycle gas turbine (GT), where the high temperature SNG prodduction. The specs of the sulphur removal with acti-
flue gases from the GT are used for further steam production vated carbon were the same but the biosyngas composition
608 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

Fig. 7. T-Q Diagrams for flue gas heat after gas turbine and steam production in the HRB, Case B2a (left) and B2b (right).

Table 10
Gasification and Power to MeOH plant -Energy conversion efficiency.

B2a with steam B2b with steam B2a purge -GT B2b purge -GT
Offgas-HRB Offgas-HRB

*m fuel/air GT (kg/s) e e 0.23/6.7 0.35/7.62

**m fuel/air HRB (kg/s) e e 0.081/1.2 0.086/1.2
Steam (MWth) 1.498 3.123 1.498 þ 5.813 3.123 þ 5.828
Steam (% of MeOH) 2.30 3.24 11.24 9.30
Electricity GT(MWe) e e 2.745 3.136
Electricity input (MWe) 43.793 101.226 41.048 98.091
CFE(%) 52.04 52.78 53.20 53.70
ECE G&PtF(%) 53.23 54.50 59.19 58.71

* Mol % H2 N2 H2O CO2 CO CH4 CH3OH C2H4

4.3-B2a 20.72 20.78 0.03 1.05 6.14 38.64 1.6 11.03

4.3-B2b 28.72 17.50 0.13 4.26 4.37 33.09 1.37 10.55
**Mol % H2 N2 H2O CO2 CO CH4 CH3OH C2H4
5.3-B2a 8.19 8.12 0.14 6.41 1.07 31.73 9.35 3.37
5.3-B2b 9.84 5.07 0.52 24.07 0.60 23.95 8.10 27.79

before and after the units changes according to the inclusion or
not of the water gas shift and the AGR process.

Acid gas removal Unit 2: In terms of process steps and sequence
these units are the same for the two processes, but in the
modelling scheme they have different implemented process
parameters. The AGR unit is in the case of the methanol only
modelled with MDEA. The AGR unit has considerably lower
requirements in the case of methanol, when cases 1 with gasi-
fication at 800  C and 5 bar are considered. Methanol case had a
capture ratio of 81.81% with MDEA and the mass flow of
captured CO2 was equal to 0.58 kg/s, while in the SNG case a
capture ratio of around 90% and removal of 0.793 kg/s of CO2
was required [5]. For the gasification at 1000  C and 20 bar, the
two routes were modelled with a different AGR process but in
terms of mass flow of captured CO2, they had considerable dif-
ferences: 2.201 kg/s for methanol Case B2a and 3.34 kg/s for the
SNG Case A2a.

Compression Unit 3: The results and the modelling of the
compression unit are completely different in the two processes.
The first reason is the different mass flows treated and secondly
the pressure required in the downstream catalytic process is
different.

Catalytic Unit (4 and 5 for methanol and 6 for SNG) (different):
The process scheme for the fuel production is completely
different in the two processes.
Due to the above explained reasons, the results of the methanol
process are different than those of methanol. The overall system
was based on the same biomass energy input and biosyngas pro-
duction for all cases studied. In addition for the cases sized ac-
cording to oxygen demand, they also had the same electrolyser
capacity. Thus, cases A1a, A2a and B1a, B2a are directly comparable
in regard to their energy input. However, cases A1b, A2b and B1b,
B2b have only the same biomass input as common basis. In addi-
tion, the heat optimization studied for the optimum cases in both
fuels is considerably different due to the different energy needs of
the processes and fuel production in each case studied as analysed
below.
For the production of SNG via the combined concept, Case A1a
and Case A1b had the same biomass input with the Cases B1a and
B2a that were investigated in this work [5]. The cold fuel efficiency
was equal to 63.43% (Case A1a), and 57.67% (Case A1b) for the case
of SNG [5], while for methanol it was equal to 42.82% (Cases B1a)
and 46.77% (Cases B1b) respectively. For low temperature steam
oxygen gasification, the combined concept showed a lower con-
version in the methanol case. Respectively, for the higher temper-
ature gasification cases, the cold fuel efficiency was equal to 58.35%
(Case A2a), and 55.60% (Case A2b) for the case of SNG [5], while for
methanol before optimization it was equal to 52.04% (Cases B2a)
and 52.78% (Cases B2b) respectively. After optimization of the
methanol cases, the cold fuel efficiency was equal to 53.2% (Cases
B2a) and 53.7% (Cases B2b). In all cases, it is concluded that the
combined steam -oxygen gasification with electrolysers has higher
cold fuel efficiencies for the case of SNG production. Comparing the
fuels on the basis of 100% biomass input and the same installed
electrolyser capacity, thus Case A1a and Case B1a as well as Case
 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 609

Table 11
Comparison of combined concept based on a 50MWth SNG and 50MWth Methanol production.

Comparison of two considered fuels produced via Combined Gasification and Power to Fuel e Basis:50 MWth

Specification Unit SNG [5] SNG [5] MeOH MeOH

Case A1a Case A1b Case B2a Case B2b

Solid Fuel Input MJth/kg H2 510.96 108.41 370.96 155.99

Total Fuel Production MJth/kg H2 448.43 173.69 297.17 185.03
Syngas & Compression Work MJel/kg H2 4.894 4.175 9.69 5.65
Gasification & Gas Cleaning system MJel/kg H2 3.135 0.627 2.46 0.90
Electrolyser Work MJel/kg H2 187.98 187.98 187.98 187.98
GT Power MJel/kg H2 e e 12.54 6.03
Cold Fuel effciency % 63.43 57.67 53.2 53.7
CO2 utilisation indirect indirect indirect indirect
(ton CO2/ton product) 2.74 1.37
(ton CO2/GWhth product) 198 248
Direct CO2 emissions (kg/MWh product) 162.3 0 159.3 27
Installed Electrolysers for 50MWth Product MWe 20.96 54.11 31.63 50.80
Energy Storage (96% availability)a GWhe/year 183.8 466.7 283.19 442.09
a
Based on power input.

A2a with Case B2a, it can be seen that in all cases methanol has a
lower fuel production and slightly higher power consumption due
to mainly compression unit and other auxiliaries. The only case that
methanol could compete the SNG production in the combined
process scheme is when almost methane and C2þ hydrocarbons
free gas would be delivered to the synthesis unit. In this regard,
oxygen entrained flow gasification and an optimum sizing of water
gas shift and water electrolysis unit is recommended for methanol
synthesis.
Furtheron, the comparison is based on the same fuel production
output of 50 MWth and on the best cases for the production of SNG
and methanol production. The main results are presented in
Table 11. It is noted that the cases are named according to the
previous presented cases but only the relative factors are used such
as the main energy streams per kg of hydrogen and the cold fuel
efficiency, while the sizing of electrolysers does not match the
oxygen needs or the oversized cases presented before.
Another aspect of the comparison of the two fuels, which is
often confused is the CO2 utilisation. Although when the compar-
ison is based on ton per fuel the SNG has a higher CO2 utilisation,
when the comparison is based on the LHV of the product, methanol
has a higher CO2 utilisation as shown in Table 11. In comparison
with other process such as power to methanol [6e8] or the direct
use of CO2 together with natural gas for methanol production [24],
the combined scheme is an indirect CO2 utilisation process, as it
uses the CO2, which would be otherwise emitted towards increase
renewable fuel production. Comparing the direct CO2 emissions, in
the SNG case where an AGR is used (Case A1a), there are direct
biogenic emissions in the production process, which are also higher
than the methanol case based on the fuel energy output. For
methanol, even if the full carbon content of the biomass is used in
Case B2b, there are emissions deriving from the combustion of
purge and off gases. These emissions account for 27 ton CO2/GWhth
in the case B2b with full carbon content of biomass used, while for
the case B2a, these are 37.4 ton CO2/GWhth. For the case B2a, the
direct emissions from the AGR are equal to 121.9 ton CO2/GWhth,
which in sum are equal to 159.3 ton CO2/GWhth. Another important
note is the comparison between Case A1b and Case B2b, for the 50
MWth fuel production, a slightly lower electrolyser capacity is
needed for the methanol case. This would result in less electricity
import for the same fuel production and as methanol prices have
higher values than SNG, the methanol case would be more cost
competitive option in comparison to SNG.
4. Conclusions
The production of methanol was investigated in 4 different
scenarios and capacities of a combined gasification and power to
fuel technology system. MDEA was investigated for the pre com-
bustion capture in relevant cases, while water gas shift was not
required in the overall scheme. The amount of methane, ethane and
Cþ hydrocarbons varies according to the gasification conditions. It
was shown that the high content of methane, ethane and Cþ hy-
drocarbons highly influences the methanol production. Thus, for
the production of methanol and other liquid fuels with recycling
catalytic synthesis, high temperature and high pressure gasification
is recommended. The cold fuel efficiency for cases B1a and B1b, and
B2a and B2b is 42.82%, and 46.77%, and 52.04% and 52.78%
respectively. Comparing the low pressure and low temperature
gasification process (Case B1 - 5 bar/800  C) and the gasification in
higher pressure and temperature (Case B2 - 20 bar/1000  C) it is
shown that a higher electrolyser capacity is required for the latter
compared to the biomass energy input; while the methanol pro-
duction is also higher for the gasification in higher pressure and
temperature (Case B2 - 20 bar/1000  C). Optimum heat utilisation
was investigated for the cases B2a and B2b with higher methanol
production, where the sensible heat from gasification and subse-
quent cooling processes as well as the demands of distillation and
capture were considered. The utilisation of the highly energetic
purge stream either towards further production of methanol, via its
use in the gasification process or for further heat/steam production
is of major importance for the overall efficiency of the process. The
combustion of the purge stream in a gas turbine and its hot flue
gases with additional combustion of the off gases in the HRB were
further investigated. The open cycle, where the purge stream was
combusted had a net efficiency of 31.69% for case B2a and 31.75% for
case B2b. It was shown that steam production can be achieved
inside the process but also by the use of high temperature flue gases
from the gas turbine and further combustion of gas losses from the
distillation in the heat recovery boiler. Due to the additional power
provided by the gas turbine, the cold efficiency was improved
resulting in 53.2% and 53.7% for case B2a and B2b respectively. The
total energy conversion efficiency was equal to 59.19% and 58.71%
for case B2a and B2b respectively. Finally, a comparison with the
SNG production via the combined process scheme was presented
for the same fuel input and for the same fuel production. It was
concluded that SNG production has higher efficiencies than
methanol production.
610 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611

Author’s note
The same methodology and approach as presented in the pre-
sent paper, was used for the investigation of SNG production as
published in Ref. [5]. The work for both papers has been performed
in the framework of the PhD thesis entitled “Production of Sub-
stitute Natural Gas and Methanol for energy storage” submitted by
the author Dr. Efthymia Ioanna Koytsoumpa at the School of Me-
chanical Engineering at the National Technical University of Athens
in June 2017 The authors consider the present work as a follow up
and comparison of methanol and SNG production based on a
combined biomass gasification and electrolysis system.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Efthymia Ioanna Koytsoumpa: Conceptualization, Methodol-
ogy, Software, Validation, Formal analysis, Investigation, Data
curation, Writing - original draft, Writing - review & editing,
Visualization, Project administration. Sotirios Karellas: Supervi-
sion, Writing - review & editing. Emmanouil Kakaras: Writing -
review & editing, Supervision.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.renene.2020.05.169.
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 E.I. Koytsoumpa et al. / Renewable Energy 158 (2020) 598e611 611

WGS: Water Gas Shift MWh: Megawatthour electric

Nm3: Normal cubic meter
Units ppm: parts per million
Vol %: Volume per cent
%w/w: Weight to weight per cent (mass based)
bar: bar unit for P
 C: Degree Celsius unit for T
Subscripts
GW: Gigawatt
GWh: Gigawatthour
kg/s: Mass flow in kilogram per second E: Electric
kW: Kilowatt F: Fuel
kWh: kilowatt hours G&PtMeOH: Gasification & Power to Methanol
MJ: Megajoule In: Input
mol %: Mole per cent out: Output
MW: Megawatt electric th: Thermal