Article

Hydrogen-Rich Syngas Production Based on a Co-Gasification

Process Coupled to a Water–Gas Shift Reactor Without
Steam Injection
Eliseu Monteiro 1,2, * , Ouissal Bourguig 1 and Abel Rouboa 1,2,3

1 FEUP, Faculty of Engineering, University of Porto, R. Dr. Roberto Frias, 4200-465 Porto, Portugal;
[email protected] (O.B.); [email protected] (A.R.)
2 LAETA-INEGI, Associated Laboratory for Energy, Transports and Aeronautics—Institute of Science and
Innovation in Mechanical and Industrial Engineering, R. Dr. Roberto Frias, 4200-465 Porto, Portugal
3 Mechanical Engineering and Applied Mechanics of SEAS, University of Pennsylvania,
Philadelphia, PA 19104-6391, USA
* Correspondence: [email protected]

Abstract: Future decarbonized applications that rely on renewable and carbon-dioxide-neutral

hydrogen production could benefit from the gasification of waste to produce hydrogen. In the current
study, an Aspen Plus® model was developed by coupling a co-gasification model to a water–gas
shift (WGS) model. The feedstock employed in the simulations was a blend of municipal solid waste
(MSW) and biomass from Morocco. A parametric assessment was conducted to analyze the effect
of the steam-to-feedstock ratio (SFR) on the syngas composition and the WGS reactor temperature.
This study also presents a comparison between the results of the gasification process before and
after the WGS reactor, using air and steam as the gasifying agent. The results show an increase in
hydrogen volumetric percentage for higher steam-to-feedstock ratios in the gasifier. Moreover, the
inclusion of a WGS reactor enhances hydrogen and carbon dioxide while reducing the amount of
carbon monoxide in the syngas for both air and steam as the gasifying agents. It can be concluded that
a co-gasification process can be intensified by coupling it to a WGS reactor without steam injection to
produce hydrogen-rich syngas with reduced operational expenditures.
Citation: Monteiro, E.; Bourguig, O.;
Rouboa, A. Hydrogen-Rich Syngas Keywords: co-gasification; hydrogen rich syngas; water–gas shift reactor; Aspen Plus
Production Based on a Co-
Gasification Process Coupled to a
Water–Gas Shift Reactor Without
Steam Injection. Hydrogen 2024, 5, 1. Introduction
919–928. https://doi.org/
The optimal use of biomass for energy production requires good knowledge and mas-
10.3390/hydrogen5040048
tery of the raw material in terms of its technical characteristics and potential. According to
Academic Editor: Adolfo Iulianelli the National Roadmap for Energy Valorization from Biomass, an assessment of the sectors
Received: 5 October 2024
of agriculture, forestry, municipal solid waste (MSW), and wastewater has identified the
Revised: 29 October 2024
main energy potential from biomass in Morocco [1]. The total technical primary energy
Accepted: 18 November 2024
potential in 2015 was roughly 13.4 TWh per year, of which 6.6 TWh/year came from agricul-
Published: 20 November 2024 ture, 3.5 TWh/year came from forestry, 3.1 TWh/year came from waste, and 0.2 TWh/year
came from wastewater [1]. These statistics show the importance of the agricultural and
waste sectors for their technical energy potential, as well as the concentration of potential
in the northern regions of Morocco. The regions of Fes-Meknes and Casablanca-Settat have
Copyright: © 2024 by the authors. the greatest potential. While the potential in Casablanca-Settat is based mainly on organic
Licensee MDPI, Basel, Switzerland. household waste and green waste, the potential in Fes-Meknes is characterized by potential
This article is an open access article
from agriculture [2]. Morocco has approximately 7 million head of cattle and a forestry
distributed under the terms and
area of approximately 9 million hectares. This represents a large biomass potential, which,
conditions of the Creative Commons
along with the MSW, can be used as feedstock in biomass power plants [3]. Population
Attribution (CC BY) license (https://
growth, rising living standards, and urbanization all contribute to Morocco’s rising waste
creativecommons.org/licenses/by/
production. MSW management is one of Morocco’s most pressing environmental issues.
4.0/).

Hydrogen 2024, 5, 919–928. https://doi.org/10.3390/hydrogen5040048 https://www.mdpi.com/journal/hydrogen

Hydrogen 2024, 5 920

More than five million tons of MSW are generated each year, and a 3% yearly growth rate
is forecasted for the country [4]. This means that Morocco’s MSW production will rise to
around 9.30 million tons in 2030 [2].
MSW disposal in Morocco can be solved by providing adequate resources and infras-
tructure. One of the suitable infrastructures to implement may involve the use of thermal
technologies (e.g., incineration, pyrolysis, and gasification) to extract energy from MSW [5].
Biagini et al. [6] performed a comparative study to assess the suitability of combustion,
gasification, electrolysis, and syngas separation processes for hydrogen generation from
biomass. They concluded that a greater amount of hydrogen is generated when using
the gasification/separation processes, followed by gasification/electrolysis, and lastly by
combustion/electrolysis processes. Monteiro and Brito [7] reviewed hydrogen production
technologies from fossil fuels and renewable energy sources. They concluded that the most
economical technologies for hydrogen production are partial oxidation, steam methane
reforming, coal gasification, and biomass gasification. Thus, the gasification of biomass has
been considered as one of the most efficient pathways for hydrogen generation [8,9].
Waste gasification is a thermal process that occurs in a substoichiometric atmosphere
at temperatures ranging from 800 to 1200 ◦ C [10,11]. The gas produced by gasification
is generally known as syngas, and it can be used to make chemicals or transformed
into fuels like hydrocarbons or hydrogen [12]. Because of the complexity of the biomass
gasification process, modeling and simulation are helpful tools as a first approach to a
biomass gasification project [13]. In this regard, Aspen Plus® has been extensively used in
the development of various gasification models to optimize hydrogen production, mainly
because of its extensive library of properties and operating units [14].
Singh and Tirkey [15] investigated the steam plasma gasification of medical waste
in Aspen Plus® . They concluded that if steam is used as the gasifying agent, it will
increase the amount of hydrogen in the syngas. Bourguig et al. [16] enlarged the parametric
analysis, developing a co-gasification plant model in Aspen Plus for hydrogen production
from municipal solid waste and biomass mixtures. Their main findings show an increase
in hydrogen molar fractions for higher temperatures and SFR ratios. Kakati et al. [17]
developed experimental work and an Aspen Plus model of steam gasification to study
the production of hydrogen-rich syngas. They obtained a maximum hydrogen yield of
37.12% for a steam-to-biomass ratio of 0.35. Cao et al. [18] enlarged the analysis to different
gasifying agents (air, oxygen-enriched air, air/steam, and oxygen-enriched air/steam)
when developing a detailed Aspen Plus® model for biomass gasification. They concluded
that a rise in oxygen percentage leads to an increase in H2 production. The maximum H2
content was obtained when oxygen-enriched air/steam was used as a gasifying agent.
As can be seen, the optimization of hydrogen production in a gasification scenario
is generally based on a parametric study, while process intensification is very rarely ap-
proached. The following are the sole examples of research on gasification process intensifi-
cation for the increase of hydrogen production. Novais et al. [19] developed an air-blown
gasification model in Aspen Plus® , integrating a water–gas shift reactor without catalysts
to study its optimization. The gasifier was optimized for carbon monoxide or hydrogen
production and compared to the steam gasification process. They concluded that coupling
a WGS reactor with an air-blown biomass gasification process results in 52.5% hydrogen
molar fractions in syngas while using lower steam flow rates than those of the steam
gasification process. Pala et al. [20] used Aspen Plus® to create a simulation model of steam
biomass gasification and subsequent syngas adjustment using a water–gas shift reactor.
They concluded that the H2 and CO concentrations were changed in such a way that the
H2 /CO ratio was adjusted to a value close to the 2.15 needed for Fischer–Tropsch synthesis.
Chu et al. [21] investigated hydrogen generation from syngas with a high carbon dioxide
content using a water–gas shift reactor in Aspen Plus® . The Cu-Zn and Fe-Cr catalysts
were used to increase hydrogen yield, and the influence of velocity, temperature, and
H2 O/CO ratio were studied. They concluded that both catalysts are suitable for syngas
water–gas shift reactions at high CO2 concentrations. At 450 ◦ C, the maximum value of H2
Hydrogen 2024, 5 921

increase occurs, which is unaffected by the increase in CO2 . Ersoz et al. [22] established
an integrated model in Aspen Plus involving a bubbling fluidized bed reactor, a syngas
cleaning and conditioning unit (hydrocarbon reforming and water–gas shift processes),
and a pressure swing adsorption unit to isolate the hydrogen from the syngas stream. The
syngas obtained had 38.8% H2 and 1.65% CO. Mojaver and Khalilarya [23] developed an
integrated system comprising a gasifier reactor, steam methane reformer, and water–gas
shift reactor, intended to convert face mask waste into a hydrogen-rich syngas. Their results
indicate a cumulative increase of 160% in hydrogen content and a reduction in methane
content and carbon monoxide of 38.4% and 78.8%, respectively.
As previously noted, the current approach to enhancing the hydrogen content in
the syngas involves the coupling of a WGS reactor with additional steam supply. Given
that steam production is an energy-intensive and thus expensive process, the novelty of
this work is the investigation into improving hydrogen production from a co-gasification
process coupled to a water–gas shift reactor without steam injection, making use of the
steam generated by moisture evaporation.

2. Materials and Methods

2.1. Feedstock Characterization
The feedstock selected to feed the co-gasification process is a blend of organic MSW
and biomass characteristic of Moroccan waste products. The co-gasification feedstock
was defined to maximize the hydrogen amount in the syngas according to the findings of
Bourguig et al. [16]. Therefore, the feedstock mixture is comprised of 70% MSW and 30%
biomass, the ultimate and proximate analyses of which are depicted in Table 1.

Table 1. Composition of the feedstock mixture [16].

Ultimate Analysis (wt.%, d.a.f.) Proximate Analysis (wt.%)

C 55.23 Volatile Matter 64.4
H 8.04 Fixed Carbon 12.6
N 1.99 Moisture 19.8
O 34.74 Ash 3.2

The oxygen content was calculated in Bourguig et al. [16] by subtracting it from the
other elements in the ultimate analysis on a dry and ash-free basis, as shown in Table 1.

2.2. Model Description

The developed simulation model comprises two main processes: the co-gasification
process and a water–gas shift process. The former is modeled according to the model
developed in a previous publication by Bourguig et al. [16]. The latter is added in this
study to the simulation model as a WGS reactor (WGSR). The entire model is built on
thermodynamic equilibrium and on the following methods and assumptions [24,25]:
• The model is based on the non-stoichiometric method.
• The model is in a steady state.
• The processes are isothermal and isobaric.
• Char is assumed to contain only carbon.
• Gases behave as ideal gases.
• Ashes and tars are disregarded in the process.
Drying, pyrolysis, and gasification are the main steps used to simulate the co-gasification
process. The Aspen Plus flowchart of the model developed by Bourguig et al. [16] is shown
in Figure 1.
Hydrogen 2024, 5, FOR PEER REVIEW 4
Hydrogen 2024, 5 922
Hydrogen 2024, 5, FOR PEER REVIEW 4

Figure 1.
Figure Flowchartof
1. Flowchart ofthe
theco-gasification
co-gasificationprocess
process developed
developed in
in Aspen
Aspen Plus
Plus[16].
[16].
Figure 1. Flowchart of the co-gasification process developed in Aspen Plus [16].
The simulation employs two types of components: conventional and non-conventional.
The simulation employs
The simulation employstwo two typesofofcomponents:
components: conventional andand non-conven-
The thermodynamic properties oftypes conventional components conventional
are computed non-conven-
using Peng–
tional.
tional. The thermodynamicproperties
The thermodynamic propertiesofofconventional
conventional components are
components computed using
Robinson–Boston–Mathias’s equation of state (PR-BM). This modelare is computed
suitable when using work-
Peng–Robinson–Boston–Mathias’s
Peng–Robinson–Boston–Mathias’s equation
equation ofof state
state (PR-BM).
(PR-BM). ThisThis model
model is is suitable
suitable when when
ing with gasification at high temperatures [26,27]. The density and enthalpy of non-
working
working with gasification
with gasificationatathigh hightemperatures
temperatures [26,27].
[26,27]. The The density
density and enthalpy of non-
conventional solid materials are computed, respectively, using theand enthalpy
COALIGT of non-
and HCOAL-
conventional
conventional solid materials are computed, respectively, using the COALIGT and
GEN models solid [28]. The materials
wet MSW are computed,
and biomass respectively,
stream (FEED-WB) using theareCOALIGTfed into the and dryer
HCOALGEN
HCOALGEN models [28]. The wet MSW and biomass stream (FEED-WB) are fed into the the
models [28]. The wet MSW and biomass stream (FEED-WB) are fed into
block, where they are identified as non-conventional components through ultimate and
dryer
dryer block, where wherethey theyare areidentified
identifiedasasnon-conventional
non-conventional components
components through
through ultimate
ultimate
proximate analyses. The moisture in the feedstock is converted into the conventional com-
and proximate
and proximate analyses.
analyses. The
The moisture
moisture ininthe
thefeedstock
feedstock is converted
is converted intointo
the the
conventional
conventional
ponent H2 O at the stoichiometric dryer block (DRER). The stream leaving the dryer block
component H
component 2O at the
thestoichiometric dryer block (DRER). The stream leaving the the
dryer
is supplied H to2Otheatpyrolysis stoichiometric
block (PYR) dryer
andblock (DRER).
modeled as a TheYIELD stream
reactor.leavingIn this dryer
reactor,
block is
block is supplied
supplied to to the
the pyrolysis
pyrolysis block
block (PYR)
(PYR) and
and modeled
modeled as as
a YIELD
a YIELD reactor. In this
reactor. In this
the feedstock is decomposed into volatiles, char, and ash. The feedstock is then supplied
reactor, the
reactor, the feedstock
feedstock isisdecomposed
decomposed into
intovolatiles,
volatiles, char,
char,and andash.ash.
TheThe feedstock
feedstock is then
is then
to the gasification block, comprising a Gibbs reactor (RGIBBS) along with steam, which is
supplied to
supplied to the
the gasification
gasification block, comprising a Gibbs reactor (RGIBBS) along withwithsteam,
used as the gasifying agentblock,
in thiscomprising
process. Aadetailed
Gibbs reactor (RGIBBS)
description along
of this steam,
co-gasification
which
which is
is used
used as
as the
the gasifying
gasifying agent
agent ininthis
thisprocess.
process. A detailed
A detailed description
description of this
of co-gas-
this co-gas-
model can
ification be found
model can be in a previous publication by Bourguig et al. [16].
ification
In model
this canthe
study, befound
foundinina aprevious
co-gasification previous
model
publication
publication
is further
byby Bourguig
Bourguig
developed
et al.
et [16].
al. [16]. a water–gas
byincluding
including
In this study, the co-gasification model is further developed by a water–
In
shiftshiftthis
reactor study,
(WGSR) the co-gasification
to try model is further developed by including a content,
water–
gas reactor (WGSR) to to
tryenhance
to enhance the quality of the
the quality of syngas
the syngas in terms
in termsof hydrogen
of hydrogen
gas shift reactor
avoidingavoiding (WGSR)
the addition to try to
of steamoftosteamenhance
the WGSR the quality
to decrease of the syngas
the operational in terms of
expenditures.hydrogen
content, the addition to the WGSR to decrease the operational expend- The
content,
new Aspenavoiding
Plus the addition
flowchart of of steam
the entire to the WGSR
model is shown to decrease
in Figure the
2. operational expend-
itures. The new Aspen Plus flowchart of the entire model is shown in Figure 2.
itures. The new Aspen Plus flowchart of the entire model is shown in Figure 2.

Figure 2.
Figure Flowchartofofthe
2. Flowchart theco-gasification
co-gasification model
model coupled
coupled to atowater–gas
a water–gas
shiftshift reactor.
reactor.
FigureThe
2. Flowchart of the co-gasification
syngas coming model coupled
from the separator (SEP2) to a water–gas
enters the heatshift reactor. (COOLER1)
exchanger
The syngas coming from the separator (SEP2) enters the heat exchanger (COOLER1)
to adjust
to adjust its
itstemperature
temperaturetotothat thatofof
thethe WGSR.
WGSR. Then,
Then, thethe syngas
syngas is supplied
is supplied to reactor
to the the reactor
The syngas coming from the separator (SEP2) enters the heat exchanger (COOLER1)
(WGSR). In this reactor, the water–gas
the water–gas shift reaction, also known as the Dussan
Dussan reaction [29],
to adjust
occurs. its temperature
It is aIt chemical to that
reaction of the
thatthat WGSR.
converts Then, the
a combination syngas is
of carbon supplied
monoxide to theandreactor
steam
[29], occurs. is a chemical reaction converts a combination of carbon monoxide and
(WGSR).
into a intoIn this reactor,
combination the water–gas
of carbon dioxide shift
and reaction,as
hydrogen, also known
follows [30]:as the Dussan reaction
steam a combination of carbon dioxide and hydrogen, as follows [30]:
[29], occurs. It is a chemical reaction that converts a combination of carbon monoxide and
◦ hydrogen, as follows [30]:
steam into a combination
CO + H2ofO carbon + H2 ∆H
↔ CO2dioxide and
(298 K) = −41.09 kJ/mol (1)
Hydrogen 2024, 5 923

Equation (1) shows that the WGS reaction is reversible and moderately exothermic. To
enable large-scale hydrogen production from syngas, a suitable catalyst must be used to
promote the WGS reaction [30]. Pal et al. [31] offer a very complete overview of the various
types of WGS reaction catalysts. Moreover, practical applications of the WGS reaction
are conducted using two adiabatic stages: the high temperature shift followed by the low
temperature shift [32]. Usually, iron-chromium and copper-zinc catalysts have been used to
boost the reaction at high and low temperatures, respectively. Copper-based catalysts used
for low temperature shift reactions are prone to poisoning by the sulfur compounds present
in some biomass sources, such as the MSW used in this work, whereas the iron-based
catalysts are more robust and sulfur-tolerant [33,34]. A detailed discussion on various high
temperature and low temperature shifts and other metals and nanomaterial catalysts is
offered by Pal et al. [31]. The WGSR is herein modeled based on a thermodynamic approach
referred to as a Gibbs reactor (RGibbs), which models single-phase chemical equilibrium, or
simultaneous phase and chemical equilibria (non-stoichiometric), by minimizing the Gibbs
free energy [35]. The input parameters are the reactor temperature and pressure. After
the WGS reaction, the produced gas goes through a second heat exchanger (COOLER2) to
reject the surplus heat, which can be used, along with the heat rejected in the COOLER1, for
district heating applications [36]. Finally, a separator (SEP3) is used to detach byproducts
from pure syngas, which is rich in hydrogen. Table 2 shows the input parameters used in
the WGS model.

Table 2. Aspen Plus® inputs used in the WGS model [37].

Unit Name Block ID Aspen Plus Unit Input

Syngas cooling COOLER Heater 200 < T < 700 ◦ C; 1 atm
WGS reactor WGSR RGibbs 200 < T < 700 ◦ C; 1 atm
Separator SEP Flash 1 atm; Duty = 0 kW

2.3. Model Validation

The gasifier block model developed was validated against two experimental results
of Jayah et al. [38] on rubber wood gasification under different conditions. Proximate and
ultimate analyses of rubber wood are shown in Table 3.

Table 3. Proximate and ultimate analysis of rubber wood [38].

Proximate Analysis (wt.%. d.b.) Ultimate Analysis (wt.%, d.b)

Volatile matter 80.1 C 50.6
Fixed carbon 19.2 H 6.5
Ash 0.7 O 42.0
N 0.2

A comparison between the experimental results of Jayah et al. [38] for a temperature
of 1100 K and the conditions is expressed in Table 4.

Table 4. Summary of gas analyses from three gasification experiments [32].

Chip Size Moisture Air/Fuel

Experiment H2 CO CO2 N2
(cm) (%) Ratio
1 4.4 16.0 1.96 17.0 18.4 10.6 52.7
2 5.5 14.7 1.86 15.5 19.1 11.4 52.9

The deviation of the Aspen Plus results from the experimental results is quantified
using the relative error, defined as follows:

Experimental value − Numerical value

Rel. Error(%) = × 100 (%) (2)
Experimental value
 The deviation of the Aspen Plus results from the experimental results is quantified
using the relative error, defined as follows:

Experimental value Numerical value (2)

Rel. Error % 100 %
Hydrogen 2024, 5 Experimental value 924

The gasification model developed can be considered validated once it achieves re-
sults that
Theagree well with
gasification modelthedeveloped
experimental data
can be [38]. It is validated
considered noted thatoncethe itrelative error
achieves is
results
below 16.7%well
that agree for the
withmain gas species present
the experimental in the
data [38]. It issyngas
noted(Table 5).relative
that the This can be consid-
error is below
ered a good
16.7% approximation
for the since present
main gas species the Aspen Plussyngas
in the model(Table
approach usedcan
5). This in this work ne-
be considered
a good
glects someapproximation since thefeatures,
biomass gasification Aspen Plus
suchmodel
as the approach used
particle size, in this work
chemical neglects
kinetics, and
some
fluid biomass Earlier
dynamics. gasification features,
published such
works as the
found particle
similar size, chemical
relative kinetics, and fluid
errors [39,40].
dynamics. Earlier published works found similar relative errors [39,40].
Table 5. Comparison between Aspen Plus results and literature experimental results.
Table 5. Comparison between Aspen Plus results and literature experimental results.
Data H2 CO CO2 N2
Experiment
Data 1 H2 17.0 CO18.4 CO 10.6
2 52.7
N2
Aspen Plus model
Experiment 1 (%) 17.0 15.78 18.420.64 9.72
10.6 53.86
52.7
Relative
Aspen Error(%)
Plus model (%) 15.78 7.2 20.64−12.2 8.3
9.72 −2.2
53.86
Relative Error (%)2
Experiment 7.2 15.5 −12.2 19.1 8.3
11.4 −2.2
52.9
Experiment
Aspen 2
Plus model (%) 15.5 14.97 19.120.50 11.4
13.30 52.9
50.32
Aspen
Relative Error(%)
Plus model (%) 14.97 3.4 20.50−7.3 13.30
−16.7 50.32
4.9
Relative Error (%) 3.4 −7.3 −16.7 4.9

3. Results and Discussion

3. Results and Discussion
In order to analyze the effect of the co-gasification process parameters on syngas
In order
composition to adding
after analyzeathe effect ofshift
water–gas the reactor,
co-gasification process
a sensitivity parameters
analysis on syngas
to the steam-to-
composition after adding a water–gas shift reactor, a sensitivity analysis
feed ratio (SFR) was performed. Moreover, the co-gasification process using air and steam to the steam-
to-feed ratio (SFR) was performed. Moreover, the co-gasification process
as the gasifying agents is compared before and after the WGSR. The co-gasification pa- using air and
steam as the gasifying agents is compared before and after the WGSR. The
rameters are fixed to maximize the hydrogen amount in the syngas according to the find- co-gasification
parameters
ings are fixed
of Bourguig to maximize
et al. [16]. Therefore,thethe
hydrogen amount
gasification in the syngas
temperature is fixedaccording
at 750 °Ctoandthe
findings of Bourguig et al. [16]. Therefore, the gasification temperature is fixed at 750 ◦C
the feedstock mixture comprises 70% MSW and 30% biomass, as shown in Table 1.
and the feedstock mixture comprises 70% MSW and 30% biomass, as shown in Table 1.
3.1. Effect of the SFR
3.1. Effect of the SFR
The steam-to-feedstock ratio plays an important role in the gasification process,
The steam-to-feedstock ratio plays an important role in the gasification process, mainly
mainly because it enhances
because it enhances the hydrogen
the hydrogen content
content of the of the syngas
syngas [15,16].
[15,16]. FigureFigure 3 shows
3 shows the
the results
results obtained after adding different amounts of steam to the gasifier in order to reveal
obtained after adding different amounts of steam to the gasifier in order to reveal the effect
the
of effect
steamof steam concentration
concentration oncomposition.
on syngas syngas composition.

Figure 3. Effect of SFR on syngas composition.

Figure 3. Effect of SFR on syngas composition.
Figure 3 shows that H2 and CO2 volume fractions increase, while the CO volume
fraction decreases with increasing SFR. According to the Le Chatelier principle [41], the
WGS reaction is favored in the forward direction as the concentration of the reactants (i.e.,
steam) increases. The results showed that the effect of the SFR on hydrogen concentration is
relevant. Additionally, it is observed that the WGS reactor enhances the hydrogen content
in the syngas and reduces the amount of carbon monoxide. These results are corroborated
by the results of Pala et al. [19].
 tion
tiondecreases
decreaseswithwithincreasing
increasingSFR. SFR.According
Accordingto tothe
theLe
LeChatelier
Chatelierprinciple
principle[41],
[41],the
theWGS
WGS
reaction
reaction is favored in the forward direction as the concentration of the reactants (i.e.,
is favored in the forward direction as the concentration of the reactants (i.e.,
steam)
steam)increases.
increases.The
Theresults
resultsshowed
showedthatthatthe
theeffect
effectof
ofthe
theSFR
SFRononhydrogen
hydrogenconcentration
concentration
isisrelevant.
relevant.Additionally,
Additionally,ititisisobserved
observedthat
thatthe
theWGS
WGSreactor
reactorenhances
enhancesthe
thehydrogen
hydrogencon-con-
Hydrogen 2024, 5 tent
tentininthe
thesyngas
syngasand
andreduces
reducesthe theamount
amountof ofcarbon
carbonmonoxide.
monoxide.These
Theseresults
resultsare
arecorrob-
corrob-
925
orated
oratedby bythetheresults
resultsof
ofPala
Palaet etal.
al.[19].
[19].

3.2.
3.2.Effect
Effectofofthe
Effect theWGSR
WGSR
Temperature
Temperatureplays playsananessential
essentialrole
roleininthe
theWGS
WGSreaction.
reaction.This
Thisreaction
reactionisismoderately
moderately
exothermic and
exothermic and its its equilibrium
its equilibrium constant
equilibriumconstant decreases
constantdecreases
decreases with
with increasing
increasing
with temperature.
temperature.
increasing The
temperature.Thereac-
reac-
The
tion
tionisisfavored
reaction favored thermodynamically
is favored thermodynamically
thermodynamically atatlower temperatures
at lower
lower temperatures
temperatures and
andkinetically
and at
atelevated
kinetically
kinetically tem-
at elevated
elevated tem-
peratures
peratures[30,31].
temperatures [30,31]. Therefore,
[30,31].
Therefore, the
Therefore, temperature
thethe temperature
temperature range that
range
range maximizes
that
that maximizes
maximizes the hydrogen
thethe hydrogen
hydrogen yield in
yield
yield in
the
in
the WGSR
the
WGSRWGSR should
should
should be defined.
bebe defined.
defined. This isisperformed
This
This is performed
performed considering aaco-gasification
considering
considering a co-gasification
co-gasification process us-
process
process us-
ing
ingair
usingair as
air the
asas gasifying
the
the gasifyingagent.
gasifying agent.Figure
agent. Figure444shows
Figure showsthe
shows theeffect
the effectof
effect ofWGSR
WGSR temperature
temperatureon
temperature onsyngas
syngas
composition, varying the temperature between 200 ◦ C and 700 ◦ C.
composition, varying thetemperaturetemperaturebetween
between200 200°C°C and 700°C.°C.

30
30
%)
(vol. %)

25
25
compostion (vol.

20
20
Gas compostion

H2
H2
15
15
CO
CO
10
10 CO2
CO2
Gas

55

00
150
150 250
250 350
350 450
450 550
550 650
650 750
750
WGSR
WGSRtemperature
temperature(°C)
(°C)

Figure Effect
Figure4.4.Effect
EffectofofWGSR
WGSRtemperature
temperatureon
onsyngas composition.
syngascomposition.
composition.

Figure
Figure44shows
showsthat thatthe
that thevolumetric
the volumetricpercentage
volumetric percentageof
percentage ofH
of HH222and
andCOCO
CO222slightly increaseswith
slightlyincreases with
the
theincreasing
increasingtemperature
temperatureof ofthe
theWGSR,
the WGSR,while
WGSR, whileCO
while COslightly
CO slightlydecreases.
slightly decreases.The
decreases. Thetemperature
temperature
temperature
range ◦ C–600 ◦ C.
rangethat
thatmaximizes
maximizeshydrogen
maximizes hydrogenyield
hydrogen yieldis
yield isis500
500
500°C–600
°C–600°C.°C.These tendenciesagree
Thesetendencies agreewith
withthose
those
reported
reported by
by Pala
Palaet
etal.
al. [19]. Figure
[19]. 5
Figure shows
5 shows the difference
the in
difference the
in amount
the of
amount
reported by Pala et al. [19]. Figure 5 shows the difference in the amount of syngas syngas
of produced
syngas pro-
pro-
through
duced co-gasification
ducedthrough before
throughco-gasification and
co-gasificationbefore after
beforeand the WGSR.
andafter
afterthe
theWGSR.
WGSR.

Figure 5.5.Syngas
Figure5.
Figure Syngas composition
Syngascomposition before
compositionbefore and
beforeand after
andafter the
afterthe WGSR
theWGSR using
WGSRusing air
usingair as
airas the
asthe gasifying
thegasifying agent.
gasifyingagent.
agent.

As shown
Asshown
showninin Figure
Figure5,5,5,itititisisis
inFigure observed
observed
observed that
that
that the
thethewater–gas
water–gas
water–gas shift
shift
shift reactor
reactor
reactor enhances
enhances
enhances hydro-
hydro-
hydrogen
gen
and and carbon
gen carbon
and carbon dioxide
dioxidedioxide while
whilewhile
reducing reducing
reducing the amount
the amount
the amount of carbon
of carbon
of carbon monoxide.
monoxide.
monoxide. These results
These results
These results agree
with the earlier published data of Novais et al. [21]. Figure 6 shows the volume fraction of
the main syngas species obtained through the steam co-gasification before and after the
water–gas shift reactor.
Hydrogen 2024, 5, FOR PEER REVIEW 8

agree with the earlier published data of Novais et al. [21]. Figure 6 shows the volume
Hydrogen 2024, 5 926
fraction of the main syngas species obtained through the steam co-gasification before and
after the water–gas shift reactor.

Figure6.6.Syngas
Figure Syngascomposition
compositionbefore
beforeand
andafter
afterthe
theWGSR
WGSRusing
usingsteam
steamas
asthe
thegasifying
gasifyingagent.
agent.

Figure 66 shows that

Figure that the
thewater–gas
water–gasshift
shiftreaction
reactionenhances
enhances hydrogen
hydrogen and
andcarbon di-
carbon
oxide while
dioxide whilereducing
reducingthe
theamount
amountof ofcarbon
carbon monoxide
monoxide in the syngas. It also also demonstrates
demonstrates
thatthe
that theCOCOisismainly
mainlyconverted
convertedto toCO
CO22rather
ratherthan
thanHH22.. Nevertheless,
Nevertheless, itit can
can be
be concluded
concluded
thatthe
that theinclusion
inclusionof
ofaaWGSR
WGSRhas hasanan important
importantimpact
impacton onthe
the quality
qualityof of the
the syngas
syngas because
because
ititincreases
increaseshydrogen
hydrogenandandreduces
reducescarbon
carbonmonoxide
monoxidein in the
the final
final composition
composition of of the syngas.
These
Theseresults
resultsagree
agreewith
withthe
theearlier
earlierpublished
publisheddata
dataofofPala
Palaetetal.
al.[19].
[19].

4.
4. Conclusions
Conclusions
In ® that couples
Inthe
thecurrent
currentstudy,
study,a comprehensive
a comprehensive model
model is developed in Aspen
is developed PlusPlus
in Aspen ® that cou-

aples
co-gasification process of MSW and biomass to a water–gas shift reactor
a co-gasification process of MSW and biomass to a water–gas shift reactor without without steam
injection. The main purpose of this work is to understand the advantages
steam injection. The main purpose of this work is to understand the advantages of using of using a
WGSR
a WGSR to to
improve
improve syngas
syngas quality.
quality.The
Theresults
resultsshow
showan anincrease
increaseininhydrogen
hydrogenvolumetric
volumetric
percentage
percentage for higher steam-to-feedstock ratios in the gasifier. The main findings
for higher steam-to-feedstock ratios in the gasifier. The main findings ofof this
this
study clearly indicate that the inclusion of a WGSR without steam addition
study clearly indicate that the inclusion of a WGSR without steam addition increases hy- increases
hydrogen
drogen and andcarbon
carbondioxide
dioxidewhile
whilereducing
reducingthetheamount
amount of of carbon
carbon monoxide
monoxide in in the
the syngas
syngas
when
when using both air and steam as gasifying agents. This method is particularlyrelevant
using both air and steam as gasifying agents. This method is particularly relevant
for high-moisture feedstocks since the WGSR can use steam produced in the gasification
for high-moisture feedstocks since the WGSR can use steam produced in the gasification
process. Moreover, the process may be further intensified by providing additional steam
process. Moreover, the process may be further intensified by providing additional steam
to the WGSR. This would raise the steam concentration in the reactants, favoring the
to the WGSR. This would raise the steam concentration in the reactants, favoring the for-
forward WGS reaction, hence increasing CO consumption and H2 generation. However,
ward WGS reaction, hence increasing CO consumption and H2 generation. However, an
an economic assessment should be conducted on the final cost of the hydrogen due to the
economic assessment should be conducted on the final cost of the hydrogen due to the
increase in operational expenditures caused by the addition of a steam generator.
increase in operational expenditures caused by the addition of a steam generator.
Author Contributions: Conceptualization, E.M. and O.B.; methodology, A.R.; software, E.M.; valida-
Author Contributions: Conceptualization, E.M. and O.B.; methodology, A.R.; software, E.M.; vali-
tion, E.M.; investigation, O.B. and E.M.; writing—original draft preparation, O.B.; writing—review
dation, E.M.; investigation, O.B. and E.M.; writing—original draft preparation, O.B.; writing—re-
and editing, E.M.; supervision, A.R. and E.M.; project administration, A.R.; funding acquisition, E.M.
view and editing, E.M.; supervision, A.R. and E.M.; project administration, A.R.; funding acquisition,
All authors have read and agreed to the published version of the manuscript.
E.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by FCT—Foundation for Science and Technology, I.P., grant
Funding: This research was funded by FCT—Foundation for Science and Technology, I.P., grant
number 2022.08625. https://doi.org/10.54499/2022.08625.PTDC.
number 2022.08625. PTDC; . https://doi.org/10.54499/2022.08625.
Data Availability Statement: The original contributions presented in the study are included in the
Data Availability Statement: The original contributions presented in the study are included in the
article; further inquiries can be directed to the corresponding author.
article; further inquiries can be directed to the corresponding author.
Conflicts of Interest: The authors declare no conflicts of interest. The funders had no role in the design
Conflicts of Interest: The authors declare no conflicts of interest. The funders had no role in the
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or
design of the study; in the collection, analyses, or interpretation of data; in the writing of the manu-
in the decision to publish the results.
script; or in the decision to publish the results.
Hydrogen 2024, 5 927

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