ChemEngineering 05 00020

chemengineering
Article
Simulation of a Downdraft Gasifier for Production of Syngas
from Different Biomass Feedstocks
Mateus Paiva 1 , Admilson Vieira 2 , Helder T. Gomes 1 and Paulo Brito 1, *
1 Centro de Investigação de Montanha (CIMO), Instituto Politécnico de Bragança, Campus de Santa Apolónia,
5300-253 Bragança, Portugal; mateusviniciuspaiva@outlook.com (M.P.); htgomes@ipb.pt (H.T.G.)
2 Departamento de Engenharia Química, Universidade Tecnológica Federal do Paraná, Campus Londrina,
Londrina 86036-370, Brazil; lopesvieira@utfpr.edu.br
* Correspondence: paulo@ipb.pt
Abstract: In the evaluation of gasification processes, estimating the composition of the fuel gas for
different conditions is fundamental to identify the best operating conditions. In this way, modeling
and simulation of gasification provide an analysis of the process performance, allowing for resource
and time savings in pilot-scale process operation, as it predicts the behavior and analyzes the effects
of different variables on the process. Thus, the focus of this work was the modeling and simulation
of biomass gasification processes using the UniSim Design chemical process software, in order to
satisfactorily reproduce the operation behavior of a downdraft gasifier. The study was performed for
two residual biomasses (forest and agricultural) in order to predict the produced syngas composition.
The reactors simulated gasification by minimizing the free energy of Gibbs. The main operating
parameters considered were the equivalence ratio (ER), steam to biomass ratio (SBR), and gasification

temperature (independent variables). In the simulations, a sensitivity analysis was carried out, where
Citation: Paiva, M.; Vieira, A.;
the effects of these parameters on the composition of syngas, flow of syngas, and heating value
Gomes, H.T.; Brito, P. Simulation of a (dependent variables) were studied, in order to maximize these three variables in the process with
Downdraft Gasifier for Production of the choice of the best parameters of operation. The model is able to predict the performance of the
Syngas from Different Biomass gasifier and it is qualified to analyze the behavior of the independent parameters in the gasification
Feedstocks. ChemEngineering 2021, 5, results. With a temperature between 850 and 950 ◦ C, SBR up to 0.2, and ER between 0.3 and 0.5, the
20. https://doi.org/10.3390/ best operating conditions are obtained for maximizing the composition of the syngas in CO and H2 .
chemengineering5020020
Keywords: biomass gasification; downdraft gasifier; process simulation; UniSim Design

Academic Editors: Anker Jensen and
Johan Jacquemin
Received: 27 February 2021

1. Introduction
Accepted: 21 April 2021
Published: 5 May 2021
Fossil fuels are still the main sources of energy used worldwide, due to their high
energy efficiency. However, in addition to the pollution caused by the gases released, fossil
Publisher’s Note: MDPI stays neutral
energy is finite, being currently depleted fast, boosting the search and the need to use
with regard to jurisdictional claims in
renewable energies [1]. Under this context, solid biomass shows great potential to become
published maps and institutional affil- an energetic alternative to fossil energy sources. This renewable energy is abundant and has
iations. a virtually zero carbon dioxide (CO2 ) balance since the CO2 produced in power generation
is equivalent to the CO2 consumed during the growth of the plant from which the biomass
was originated [2].
Biomass is a source of energy that can potentially be obtained from forest-related
Copyright: © 2021 by the authors.
industrial wastes, such as wood chips and sawdust, as well as from agricultural wastes,
Licensee MDPI, Basel, Switzerland.
such as rice husk, straw, and sugarcane bagasse [3–6]. The amount of forest waste in
This article is an open access article
Portugal is approximately 2.2 million tons per year. Portugal is the European country
distributed under the terms and with the highest number of forest fires and the second with the most burned area. Most
conditions of the Creative Commons of the fires are caused by the use of fire to burn trash and waste. Thus, the use of forest
Attribution (CC BY) license (https:// biomass for energy production can minimize the damage to landowners, forest neighbors,
creativecommons.org/licenses/by/ and investors, as it provides a destination for waste, produces energy, and tends to reduce
4.0/). fires [2,7,8].
ChemEngineering 2021, 5, 20. https://doi.org/10.3390/chemengineering5020020 https://www.mdpi.com/journal/chemengineering

ChemEngineering 2021, 5, 20 2 of 24
Biomass gasification is the conversion of organic materials into an energetic gas, rich
in hydrogen (H2 ) and carbon monoxide (CO), through oxidation and reduction reactions at
elevated temperatures. In the evaluation of gasification processes, estimating the composi-
tion of the fuel gas for different conditions is fundamental to identify the best operating
conditions. In this way, gasification modeling and simulation provide an advance virtual
analysis of the process performance, allowing for resource and time savings in pilot-scale
process operations, as it predicts the behavior and analyzes the effects of different variables
on the process [9–14].
Thus, the focus of this work is the modeling and simulation of biomass gasification
processes using the UniSim Design chemical process software, applying the tools available
in the simulator database in order to satisfactorily reproduce the operation behavior of a
gasifier. The work is associated with a parallel project concerning the design, construction,
and test of a pilot downdraft gasifier, aiming for the energetic valorization of residual
biomass from fire-hazard areas. So, the developed model is focused specifically on the
production of syngas from complex sources represented by mixtures of carbon rich organic
wastes, which can show a variety of compositions. Hence, the chosen simulated gasifier
has a downdraft design and it will be studied for the processing of forest and agricul-
tural waste type biomasses. Optimization and sensitivity analysis will be performed to
observe the influence of significant parameters affecting the process (e.g., equivalence ratio,
steam to biomass ratio, and temperature) on the properties of the synthesis gas produced
(e.g., composition and heating value).
This gas is a mixture composed mainly of carbon monoxide (CO), hydrogen (H2 ), and
methane (CH4 ). The gas produced can be standardized in quality and is easier and more
versatile to use than the original biomass, either for fueling gas engines and gas turbines or
as a chemical raw material for liquid fuel production [15]. Gasification adds value to low
or negative value raw materials by converting them into fuels. This conversion process is
more complex than simple combustion and is influenced by many factors, such as amount
of oxidant, feedstock composition, gasifier temperature, and reactor geometry [16,17].
The main gasification reactions are shown in Table 1 [3,4,14,16,18,19].
Table 1. Main reactions involved in the gasification processes.
Gasification Step Reaction ∆H◦ (kJ/mol)

Pyrolysis Biomass → Char + Tar + Volatiles (1)
Char(s) + O2 → CO2 Carbon Oxidation (2) –394
C(s) + 0.5O2 → CO Carbon Partial Oxidation (3) –110
Oxidation CO + 0.5O2 → CO2 Carbon Monoxide Oxidation (4) –283
H2 + 0.5O2 → H2 O Hydrogen Oxidation (5) –242
C(s) + CO2 ↔ 2CO Boudouard Reaction (6) 172
C(s) + H2 O ↔ CO + H2 Reforming of Char (7) 131
Reduction CO + H2 O ↔ CO2 + H2 Water Gas Shift Reaction (8) –42
C(s) + 2H2 ↔ CH4 Hydrogasification (9) –75
CH4 + H2 O ↔ CO + 3H2 Steam–methane Reforming (10) 206
The downdraft gasifier design (see Figure 1) is a reactor where the solid material
is inserted in the top and the oxidizing gas enters the reactor laterally above the grid.
The gasifying agent is introduced directly into the combustion zone, then flows into the
reduction zone, and is extracted from the gasifier. The synthesis gas exits the gasifier
after passing through the hot zone, allowing partial cracking of the tars formed during
gasification, which provides a gas with low tar. However, the gases leave the gasifier at
high temperatures (900–1000 ◦ C), leading to low efficiencies, due to the high heat content
carried by the hot gas. This reactor is suitable to convert biomass with high volatile content,
but it is limited in scale. It also needs specific biomass conditions and is not suitable for
various types of biomass [9,16].
temperatures (900–1000 °C), leading to low efficiencies, due to the high heat content
ried by the hot gas. This reactor is suitable to convert biomass with high volatile con
ChemEngineering 2021, 5, 20 but it is limited in scale. It also needs specific biomass conditions and is3not
of 24 suitable
various types of biomass [9,16].
Figure 1. Downdraft gasifier.

Figure 1. Downdraft gasifier.
In computer simulation, the processes and equipment operate following the sequence
of inputIn data,
computer simulation,
data processing, the processes
and return output data. and equipment
Usually, these data operate
are massfollowing
flows, the
quence
temperatures,of input data, data
compositions, andprocessing,
pressures. For andthereturn outputadaptation,
construction, data. Usually,or scaling these data
of equipment,
mass it is necessary tocompositions,
flows, temperatures, obtain well-dimensioned parameters.
and pressures. For theIf these actions are adapta
construction,
done without prior study, the experimental data obtained may not be satisfactory and time
or scaling of equipment, it is necessary to obtain well-dimensioned parameters. If t
and money have been spent on incorrect reactor sizing and operation [20,21].
actions are done without prior study, the experimental data obtained may not be satis
Modeling and simulation of gasification systems help in predicting the outlet gas
tory and time
composition whenand money
operating have been
conditions spent
and scale sizeon incorrect
change. reactor
This assists sizing and
in planning the opera
[20,21].
construction or retrofitting of existing equipment. UniSim Design is a chemical process
modeling software,
Modeling andwithsimulation
a similar design to that of Aspen
of gasification Plus and
systems Aspen
help in Hysys. It is used
predicting the outlet
in engineering to create dynamic and steady-state models for plant
composition when operating conditions and scale size change. This assists in planning design, monitoring,
troubleshooting, planning, and management. It is possible to build simulation processes
construction or retrofitting of existing equipment. UniSim Design is a chemical pro
in an integrated graphical environment including tools that allow the optimization of
modeling
these processes.software, with a similar design to that of Aspen Plus and Aspen Hysys.
usedIninthe engineering to create
literature, there dynamic
are studies and steady-state
of modeling and simulation models for plant
of biomass design, mon
gasification
ing,
mainly troubleshooting,
using Aspen Plusplanning,
and Aspen and Hysys management.
[1,2,4,18,22–27].ItInisthis
possible to build
work, UniSim simulation
Design
cesses in an integrated graphical environment including tools that allow thebe
will be used as an alternative software for these applications. A small-scale gasifier will optimiza
modeled
of these and simulated, in order to process several types of forest biomass and agricultural
processes.
wastes, thus giving a purpose to this residue. The type of gasifier chosen is a downdraft
In the literature, there are studies of modeling and simulation of biomass gasifica
due to the simple design, low cost, and quality of the outlet gas. Additionally, a non-
mainly usingequilibrium
stoichiometric Aspen Plusmodel and Aspen
is assumedHysys [1,2,4,18,22–27].
considering In thissystem
that the reaction work, is UniSim
in De
will be used as an alternative software for these applications.
its most stable state (lowest free energy). For this, the main hypothesis presumed is that A small-scale gasifier
be
the modeled
gasification and simulated,
reaction rates areinfast
order to process
enough and the several
residencetypes
time isoflong
forest biomass
enough to and a
reach equilibrium. This condition is met at gasification temperatures above 800 ◦ C. Thus,
cultural wastes, thus giving a purpose to this residue. The type of gasifier chosen
the largest discrepancies
downdraft due to the simplebetweendesign,
estimatedlowand experimental
cost, and quality values
of theareoutlet
foundgas. at low Addition
temperatures, where the CO and H2 fractions are overestimated and the CO2 and CH4 ,
atar,non-stoichiometric equilibrium model is assumed considering that the reaction sys
and residual carbon fractions are underestimated. This model is based on minimizing
is in its
Gibbs freemost
energystable state (lowest
to determine free composition
the product energy). For this, the
obtained andmain hypothesis
the efficiency of thepresume
that
gasifier. The advantage of this method is that there is no need for the establishment is
the gasification reaction rates are fast enough and the residence time of long
a eno
to reach
specific setequilibrium. This the
of reactions to solve condition
problem, is met atknowledge
requiring gasification temperatures
of only the approximate above 800
and ultimate analysis [11].
Thus, the largest discrepancies between estimated and experimental values are foun
Regardless of the software used for modeling and simulation of the gasification
low temperatures, where the CO and H2 fractions are overestimated and the CO2 and C
process, there is a pattern of steps that must be followed in order to successfully perform
tar, and residual
the simulation. Thesecarbon fractionsthe
steps represent arefour
underestimated.
main zones present Thisinmodel is based
a downdraft on minimi
gasifier,
Gibbs
namely:free energy
drying, to determine
pyrolysis, the and
oxidation, product composition
reduction obtainedthe
zones. Therefore, and the efficiency o
simulation
gasifier. The advantage of this method is that there is no need for the establishment
consists of several unit operation blocks and, as in this work, the process is divided into
three blocks: drying and decomposition, combustion, and gasification. In the drying and
decomposition block, the moisture content is reduced, and the biomass is decomposed into
volatile and char compounds. In the combustion and gasification block, the oxidation and
reduction reactions will be modeled, minimizing Gibbs free energy. The approach will be
non-stoichiometric, requiring the specification of the ultimate and approximate biomass
composition and the reactions involved in the process.
Chemical engineering software provides databases for conventional fluids and solids
properties. Therefore, when unconventional materials such as biomass are employed, a
strategy should be used to inform the software about the composition of the material
entering the process. The strategy that will be used in this work is to consider biomass as
a generic char material. This allows, from the approximate and ultimate analysis of the
material, the calculation of the properties of this unconventional material, hence, obtaining
the feed stream characteristics.
The next step is the drying and decomposition block, where the goal is to reduce
the moisture content of the biomass and the dried material will be converted into compo-
nents such as carbon, hydrogen, oxygen, nitrogen, and ashes, specifying the distribution
according to the ultimate and approximate analysis.
Finally, there is the combustion and gasification stage, where a Gibbs reactor will
be used to minimize Gibbs free energy by calculating the gas composition reaching full
chemical equilibrium. In this block, air will be introduced as a gasification agent. Upon
exiting this reactor, the gas produced will pass a separating block that will remove water.
Therefore, the gaseous output stream obtained from this separator contains the desired
syngas at the end of the process.
2. Simulation Model
A gasification model was constructed in UniSim Design. In this process, a series
of unit operations were selected, integrated, and sequenced in order to simulate the
entire process.
2.1. Assumptions
Some considerations were made for the construction of this model considering a
downdraft gasifier configuration:
1. The process operates in steady state;
2. The operation takes place at atmospheric pressure and all pressure losses
are neglected;
3. The produced char is 100% carbon;
4. Peng–Robinson equation of state was selected as the thermodynamic package for the
whole process;
5. Air consists of 79% N2 and 21% O2 on a molar basis;
6. N2 is a diluent and an inert gas, so it does not react;
7. Sulfur (S) and chlorine (Cl) bounded to the fuel are converted in hydrosulfuric acid
(H2 S) and hydrochloric acid (HCl), respectively;
8. Since the temperature conditions can be very different in the two reaction zones
(combustion and reduction), even for small scale gasifiers, these reaction zones are
simulated using two different reaction systems;
9. The formation of tar is significantly reduced in the process, so it is neglected during
the simulation; therefore a sufficiently high temperature is fixated in the combustion
zone (1000 ◦ C) to account for a reasonable tar degradation yield;
10. The reduction reaction zone is simulated using two Gibbs reactors in series,
operating adiabatically.
2.2. Feedstock
The selected biomass sources were hardwood chips and almond shells, considered as a
hypothetical char simulated from the parameters shown in Table 2. The input values (kg/h)
of air and steam are listed in Table 3, in addition to the conditions of process operation.
Table 2. Approximate and ultimate analysis of the biomass stocks [28,29].
Biomass Feedstock Hardwood Chips Almond Shells

Approximate analysis (wt.%)
Fixed carbon 14.191 15.870
Volatile matter 79.470 80.280
Moisture 5.393 3.300
Ash 0.946 0.550
Ultimate analysis (wt.%)
Carbon 49.316 50.500
Hydrogen 5.902 6.580
Nitrogen 0.150 0.210
Oxygen 44.614 42.654
Sulfur 0.015 0.006
Chlorine 0.003 0.050
Higher calorific value (MJ/kg) 17 18
Flow rate (kg/h) 5 5
Table 3. Input parameters in the simulation study.
Air Feedstock
Temperature 25 ◦C
Flow rate 0.3–2.4 kg/h
Steam Feedstock
Temperature 100 ◦C
Flow rate 0.18–3.6 kg/h
Operating conditions
Temperature 600–1200 ◦C
Pressure 1 atm
2.3. Simulation Basis Manager

The Simulation Basis Manager (SBM) is the interface of the simulation project in
UniSim Design, where the components are selected and/or constructed, packages of fluid
properties are chosen in order to assist the execution of the calculations, and sets of chemical
reactions are defined. All the data can be incorporated into the unit operations which define
the equipment that constitutes the process. UniSim Design does not consider any form of
biomass as a predefined component in its component library. In this way, the composition of
biomass was modeled by Python software using the ultimate and approximate analysis to
estimate the properties of the decomposed input stream. The mass and molar composition
values of the biomass for complete decomposition are shown in Table 4.
ChemEngineering 2021, 5, x FOR PEER REVIEW 6 of 24
ChemEngineering 2021, 5, 20 Table 4. Mass and molar composition of the decomposed biomass. 6 of 24
Hardwood Chips Almond Shells

Composition (%) Mass Molar
Table 4. Mass and molar composition of the decomposed biomass.
Mass Molar
C 49.316 49.618 50.500 48.227
O2 Hardwood
39.552 Chips 14.937 Almond
39.723 Shells 14.239
Composition
H2 (%) Mass5.263 Molar
31.550 Mass6.209 Molar35.328
C 49.316 49.618 50.500 48.227
N2
O2 39.552
0.150 0.065
14.937 39.723
0.210 14.239
0.086
H22S
H 5.2630.016 0.006
31.550 6.2090.006 35.3280.002
N
HCl
2 0.1500.003 0.065
0.001 0.2100.052 0.086 0.017
H2 S 0.016 0.006 0.006 0.002
H2O
HCl 0.0035.700 3.823
0.001 0.0523.300 0.017 2.101
H2 O 5.700 3.823 3.300 2.101
2.4. Sensitivity Analysis
2.4.InSensitivity Analysis
this section will be studied the sensitivity of the model developed for a downdraft
gasifier.InThe
this section
syngaswill be studied
at the end ofthe thesensitivity
process of the model
must developed
be formed by CO,for aHdowndraft
2, and variable
gasifier. The syngas at the end of the process must be formed by
amounts of CH4, H2S, HCl, and N2. The sensitivity analysis focuses on 2,studyingCO, H and variable
the effect
amounts of CH
of the equivalence , H
4 ratio
2 S, HCl, and N 2
(ER), steam . The sensitivity analysis focuses on studying the
to biomass ratio (SBR), and gasifier temperature effect on
of the equivalence ratio (ER), steam to biomass ratio (SBR), and gasifier temperature on the
the following variables: molar composition of syngas, flow of syngas, and heating value.
following variables: molar composition of syngas, flow of syngas, and heating value.
2.5.2.5.
Model Description
Model Description
The
Theprocess
processisissimulated
simulated in three
threemain
mainsteps:
steps:drying
drying andand decomposition,
decomposition, combustion,
combustion,
and gasification. For this, a conversion reactor, Gibbs reactors, as well as other equipment
and gasification. For this, a conversion reactor, Gibbs reactors, as well as other equipment
such
such as as mixersand
mixers andsplitters
splitters were
were used.
used.The
Theflow
flowsheet is illustrated
sheet in Figure
is illustrated 2. 2.
in Figure
Figure 2. UniSim
Figure Design
2. UniSim Designflow
flowsheet
sheet for thedowndraft
for the downdraftgasification
gasification process.
process.
2.5.1. Drying
2.5.1. and
Drying andDecomposition
Decomposition
TheTheinput
inputstream
stream“Biomass”
“Biomass” waswasdefined
definedbyby Python
Python software
software fromfrom the ultimate
the ultimate and and
approximate
approximate analysis,shown
analysis, shownininTable
Table4.4.This
This streamenters
stream 500°C◦ C
entersatat500 inin
thethe splitterequip-
splitter
equipment,
ment, named named
“Water“Water Splitter”
Splitter” to separate
to separate the the water
water present
present ininthethebiomass,
biomass, leading
leading thus
thus to the streams “Dry Biomass”
to the streams “Dry Biomass” and “Water”. and “Water”.
Another Splitter equipment, named “Volatile Splitter” was used to separate volatile
Another Splitter equipment, named “Volatile Splitter” was used to separate volatile
materials from char, obtaining the streams “Volatile Materials” and “Char”. After that,
materials fromMaterials”
the “Volatile char, obtaining the streams
stream enters another“Volatile Materials”
Splitter equipment, and “Char”.
named After that,
“Acid Splitter”
thewhere
“Volatile Materials”
the acids presentstream enters another
in the volatile materialsSplitter equipment,
are separated. Thus,named “Acid
at the end Splitter”
of this
where the acids present in the volatile materials are separated. Thus,
block the currents “Volatile Feed”, “Char”, “Acid Gases”, and “Water” are obtained. at the end of this
block the currents “Volatile Feed”, “Char”, “Acid Gases”, and “Water” are obtained.
2.5.2. Combustion
This block is where the combustion reactions are simulated: carbon oxidation (2),
2.5.2. Combustion
carbon partial oxidation (3), carbon monoxide oxidation (4), and hydrogen oxidation
This block is where the combustion reactions are simulated: carbon oxidation (2),
(5), according to Table 1. For this, a conversion reactor equipment was used, named
carbon partial oxidation
“Combustor”, (3), carbon
which is operated monoxide
at 1000 ◦ C, whichoxidation (4), and
was considered hydrogenhigh
a sufficiently oxidation
value (5),
according to Table 1. For this, a conversion reactor equipment was used, named “Com-
bustor”, which is operated at 1000 °C, which was considered a sufficiently high value in
in order to ensure a reasonable tar degradation yield. The input streams in this equipment
are “Volatile Feed”, “Char”, “Air” and “Combustor Duty”. From this equipment, the
streams “Flue Gases” and “Comb Bottom” are obtained.
2.5.3. Gasification
Gasification reactions are a set of equilibrium reactions. To facilitate modeling in
UniSim Design, the set of reactions was separated into two Gibbs reactors. Both reactors
operate adiabatically for the whole analysis with the exception of the study presented in
Section 3.4, where the influence of the gasification temperature is assessed. For feeding in
the first reactor, mixer equipment, named “Mix”, was used to mix the following streams:
“Flue Gases”, “Comb Bottom”, “Acid Gases”, and “Water”, thus obtaining a unique stream
named “To Gasif” that enters the first Gibbs reactor named “Gibbs Gasificator”. The
following reactions are considered in this reactor: Boudouard reaction (6), reforming
of char (7), and hydrogasification (9), according to Table 1. The first two reactions are
endothermic and the third one is exothermic. The streams exiting this reactor are “Gasif
Gases” and “Gasif Bottom”, both of which enter the next reactor, in addition to the “Steam”
stream inlet.
In the second reactor, named “CO Shift”, two reactions are modeled: water gas shift
reaction (8) and steam–methane reforming (10), according to Table 1. The first reaction is
exothermic and the second one is endothermic. From this reactor, two streams are removed:
“Product Gases”, which enter the next equipment, and the “Solid Bottom” stream. Finally,
there is a “Splitter” device, named “Syngas Splitter” that simulates the removal of water
from the gas. This equipment has as input stream “Product Gases” and as output two
streams: “Water” and “Syngas”. The “Syngas” being the final stream, thus obtaining the
product gas at the end of the process.
3. Results and Discussion

3.1. Reference Conditions
The syngas at the end of the process must be formed by CO, H2, and small amounts
of CH4 , H2 S, HCl, and N2 . After gathering the simulated data, the model developed for a
downdraft gasifier will be compared with two case studies selected from the literature [28,30].
3.1.1. Simulation
Considering the developed model, base simulation runs were performed with each of
the two selected biomass sources (hardwood chips and almond shell). In this simulation,
the steam to biomass ratio (SBR) chosen was 0.2 for both biomass. The chosen equivalence
ratio (ER) was 0.4 for hardwood chips and 0.45 for almond shells, in which air entered the
process at 25 ◦ C and steam at 100 ◦ C as shown in Table 5.
Table 5. Parameters considered in the base simulations.
Hardwood Chips Almond Shells

Air Steam Air Steam
ER 0.40 - 0.45 -
SBR - 0.20 - 0.20
Temperature (◦ C) 25.0 100.0 25.0 100.0
Molar flow (kmol/h) 0.042 0.055 0.045 0.055
Mass flow (kg/h) 1.296 0.991 1.405 0.991
In Tables 6 and 7 are presented the main process streams, temperatures, flows (molar
and mass), syngas heating values, and molar compositions. The decomposed inlet stream
“Biomass” enters the process at 500 ◦ C with a mass flow of 5 kg/h with the compositions
determined from the ultimate and approximate analysis using the Python software, having
a high composition of C, O2, and H2 . The “Flue Gases” stream is the equipment’s output
that simulates oxidation reactions. It is observed that the stream leaves the equipment with
a fixed temperature of 1000 ◦ C. It is interesting to note that the main reaction favored was
carbon partial oxidation (3), due to the low intake of air, favoring the formation of CO. The
other reactions are favored when the amount of air for combustion is higher.
Table 6. Main simulation streams for hardwood chips.
Biomass Flue Gases To Gasif Gasif Gases Product Gases Syngas

Temperature (◦ C) 500.0 1000.0 972.5 868.5 788.7 788.7
Molar flow
0.414 0.329 0.361 0.353 0.412 0.386
(kmol/h)
Mass flow (kg/h) 5.000 5.819 6.296 6.296 7.287 6.811
HHV (MJ/kg) - - - - - 14.632
LHV (MJ/kg) - - - - - 13.501
HHV (MJ/m3 ) - - - - - 2.925
LHV (MJ/m3 ) - - - - - 2.699
C (molar %) 49.618 0.000 4.426 0.000 0.000 0.000
O2 (molar %) 14.937 0.000 0.000 0.000 0.000 0.000
H2 S (molar %) 0.006 - 0.007 0.007 0.006 0.006
HCl (molar %) 0.001 - 0.001 0.001 0.001 0.001
H2 O (molar %) 3.823 0.000 4.386 0.465 6.408 0.000
CO (molar %) - 57.570 52.492 56.488 42.063 44.943
H2 (molar %) 31.550 39.693 36.192 38.823 41.601 44.449
CO2 (molar %) - 0.000 0.000 0.579 7.319 7.819
CH4 (molar %) - - - 1.085 0.419 0.448
N2 (molar %) 0.065 2.738 2.496 2.551 2.184 2.334
Table 7. Main simulation streams for almond shells.
Biomass Flue Gases To Gasif Gasif Gases Product Gases Syngas

Temperature (◦ C) 500.0 1000.0 984.8 938.5 805.2 805.2
Molar flow
0.436 0.359 0.383 0.371 0.435 0.410
(kmol/h)
Mass flow (kg/h) 5.000 6.059 6.405 6.405 7.396 6.943
HHV (MJ/kg) - - - - - 15.477
LHV (MJ/kg) - - - - - 14.253
HHV (MJ/m3 ) - - - - - 2.923
LHV (MJ/m3 ) - - - - - 2.692
C (molar %) 48.227 0.000 3.869 0.000 0.000 0.000
O2 (molar %) 14.239 0.000 0.000 0.000 0.000 0.000
H2 S (molar %) 0.002 - 0.002 0.003 0.002 0.002
HCl (molar %) 0.017 - 0.018 0.019 0.016 0.017
H2 O (molar %) 2.101 0.000 2.389 0.084 5.781 0.000
CO (molar %) - 54.392 50.976 54.930 42.028 44.606
H2 (molar %) 35.328 42.868 40.176 40.536 43.625 46.301
CO2 (molar %) - 0.000 0,000 0.080 5.921 6.284
CH4 (molar %) - - - 1.693 0.365 0.387
N2 (molar %) 0.086 2.741 2.569 2.656 2.263 2.402
In the stream “To Gasif” all the previous streams are joined together to enter the first
reactor that simulates the reduction reactions. The temperature in the stream “To Gasif”
decreases slightly in relation to the stream that leaves the combustion equipment, due to
the lower temperatures of the other streams, entering in thermal equilibrium. This stream
contains the char that has not been volatized, the acid gases, in addition to the stream
that comes from the combustor. Therefore, an amount of C is noted, due to the char, the
presence of water, due to the biomass moisture, and also the gases already formed before
(CO, H2, and inert N2 ).
The “Gasif Gases” stream is the output of the first equipment that simulates the
reduction reactions. In this stream, it is noted that there was an increase in the composition
of CO, in addition to the formation of CH4 and all consumption of C. This is due to the
favoring of reactions such as reforming of char (7) and hydrogasification (9). The reaction
(9) is exothermic and the reaction (7) endothermic, however the reaction of reforming of
char has an enthalpy 2.3 times higher, thus the temperature in this area of the gasifier is
lower in relation to the inlet stream because there was a higher consumption of energy
compared to the energy released by the exothermic reaction.
The stream “Product Gases” is the outlet stream of the second gasifier reactor “CO
Shift” that simulates the reduction reactions. It is observed that the temperature has de-
clined in relation to the inlet stream. It is also noted that there was a rise in the composition
of H2 and CO2 , and a reduction in the composition of CH4 and CO. This behavior is due to
the fact that the steam entering the gasification step “CO Shift” favors the water gas shift
reaction (8) and steam–methane reforming (10) reactions, consuming CO, CH4, and H2 O,
to form mostly H2 and CO2 . A possible explanation for the decrease in temperature is that,
in spite of reaction (8) being exothermic, reaction (10) is endothermic with an enthalpy
five times higher. In addition, the steam enters at 100 ◦ C, so the reaction temperature is
expected to diminish through the establishment of a thermal equilibrium. The behavior
of the variations, both of the compositions and of the temperatures, was similar for the
two biomasses. The “Syngas” outlet stream has high compositions of CO and H2 , close
to 45%, and low compositions of the other components (H2 S, HCl, CH4, and N2 ). Only
CO2 showed a formation between 6 and 7%. However, with the steam inlet, it is inevitable
to favor the water gas shift reaction (8) and consequently the formation of CO2 . The feed
of steam promotes the formation of H2 , but it also has the problem of favoring the forma-
tion of CO2 . Therefore, it is advisable to work with a low steam value in order to avoid
this difficulty.
3.1.2. Literature
The results of two studies of biomass gasification reported in the literature [27,29],
one regarding the gasification of hardwood chips and the other of almond shells, are here
presented and discussed, to be compared to the study performed in this work (Table 8).
Table 8. Parameters and results of reference studies [27,29].
Studies Model 1 [27] This Work Model Model 2 [29] This Work Model
Type of biomass Hardwood chips Hardwood chips Almond shells Almond shells
Type of gasifier Downdraft Downdraft Fluidized bed Downdraft
Gasifying agent Air Air and steam Air and steam Air and steam
Software Aspen Plus UniSim Design UniSim Design UniSim Design
Pressure (atm) 1 1 1–3 1
Temperature (◦ C) 500–1000 600–1200 700–1100 600–1200
Moisture (%) 8.91 5.39 3.30 3.30
ER 0.20–0.45 0.10–0.80 0.00–1.00 0.10–0.80
SBR – 0.00–0.75 0.44–1.00 0.00–0.75
CO (%) 21.31 (41.54) * 44.94 59.60 44.61
H2 (%) 18.29 (35.58) * 44.45 23.18 46.30
CO2 (%) 11.36 (22.48) * 7.82 0.01 6.28
CH4 (%) 0.20 (0.39) * 0.45 6.12 0.39
N2 (%) 48.99 (0.00) * 2.33 8.29 2.40
* N2 -free basis.
Regarding the simulation of almond shells gasification, the gasifier selected was
a fluidized bed gasifier [29]. The gasifying agent used was air and steam. The study
was also carried out using the chemical processes simulation software UniSim Design.
The pressure varied between 1 and 3 atm and the temperature ranged between 700 and
1100 ◦ C. In the analysis of air intake, a decrease in CO and H2 was observed with a rise in
air flow. The ER varied between 0.00 and 1.00. Another parameter analyzed was steam
added to the process: SBR varied between 0.44 and 1.00, and an increase in the steam feed
led to a reduction of the CO composition and to a rise of the H2 composition. Additionally,
it was observed that the composition of CO and H2 in the syngas stream increased with
temperature value.
The simulation of the gasification of hardwood chips was carried out in a downdraft
gasifier [27]. The gasifying agent used in the process was just air. The study was done using
Aspen Plus. The pressure was fixed at 1 atm and the temperature varied between 500 and
1000 ◦ C. In the analysis of air intake, the compositions of CO, H2, and CH4 in the syngas
were found to decrease with the rise of ER, while the composition of CO2 increases with
the rise of ER. The ER varied between 0.20 and 0.45. In relation to the growth in the gasifier
temperature, the composition of the syngas increased in CO and decreased in CO2 and CH4 .
H2 behaved in such a way that its value increased until the temperature of 750 ◦ C and after
that, the composition of H2 declined. It is concluded that the recommended temperature
for the gasification is between 650 and 800 ◦ C and that the equivalence ratio is between 0.2
and 0.3 to obtain the best syngas composition parameters. Although the biomasses are of
different sub-classifications (forestry residues and agricultural solid waste), they are similar
in relation to the composition (ultimate and approximate analysis), so a similar behavior is
expected for the final composition of the syngas. If the syngas composition obtained with
the hardwood chips is presented in a N2 -free basis, the amount of CO would be 41.54%, H2
35.58%, CH4 0.39%, and CO2 22.48%. As excess air was used to obtain this syngas stream,
a considerable amount of CO2 was produced. It would be interesting to work with a low
air intake to avoid the production of CO2 and the presence of N2 in the outlet composition
of the synthesis gas produced.
Table 8 shows that the outlet gas compositions diverged from those obtained in the
almond shell study, where the amount of CO was higher (approximately 30%) compared
to our study, while the amount of H2 was lower (approximately 50%). It may be due to the
fact of considering a low amount of steam. The study with hardwood chips was closer in
terms of composition. In a N2 -free basis composition, it should be noted that CO differs 8%
and H2 20%. It is also seen that there is a large amount of CO2 (22.48%), compared to our
study (7.82%). As previously discussed, this high presence of CO2 is due to the fact that a
large amount of air is used to carry out the process.
It can be noted that both ER and SBR are parameters that significantly change the
composition of the outlet gas. For the simulations that will be presented in the next section,
low air intakes were applied in order to avoid formation of CO2 , in addition to analyzing
whether the steam input significantly interferes with the expected syngas composition.
Therefore, in the next sections, the sensitivity analysis will be carried out with the focus of
studying the effect of the equivalence ratio (ER) and of the steam to biomass ratio (SBR) on
the following variables: molar composition of the syngas, flow of syngas (molar and mass),
syngas heating value and gasifier temperature; and the effect of the gasifier temperature
on the molar composition of the syngas, flow of syngas (molar and mass) and syngas
heating value.
3.2. Effect of Equivalence Ratio

In this stage, the study of the influence of the air intake on the composition of syngas,
heating value, and gasification temperature is presented. Here the ER is the independent
variable, with the molar composition of the syngas, the flow of syngas, heating value, and
gasification temperature as dependent variables. For this study, the biomass input is fixed
at 5 kg/h, considering the same biomass input in all analyzes. In addition, the air intake
was varied up to 2.4 kg/h (approximately 0.8 ER) and there was no steam entry in the
process, only the water present in the biomass moisture was used.
at 5 kg/h, considering the same biomass input in all analyzes. In addition, the air intake
was varied up to 2.4 kg/h (approximately 0.8 ER) and there was no steam entry in the
process, only the water present in the biomass moisture was used.
ChemEngineering 2021, 5, 20 3.2.1. Molar Composition of Syngas 11 of 24
The equivalence ratio is defined as the air to biomass ratio required for gasification
divided by the stoichiometric ratio required for combustion. As the ER rises, the amount
of oxygen supplied
3.2.1. Molar to the gasifier
Composition also grows, providing a higher conversion of the carbon
of Syngas
present in Thethe fuel. However,
equivalence ratio is an excessive
defined as theamount of oxygen
air to biomass will completely
ratio required oxidize,
for gasification
leading to the decline of the fuel and the production of syngas. Therefore,
divided by the stoichiometric ratio required for combustion. As the ER rises, the amount ER is an essen-
of
tial parameter
oxygen supplied in thetogasification
the gasifier alsoprocess
grows,[4,12,27,30].
providing aFigure
higher 3 shows the
conversion effect
of the of the
carbon
equivalence
present in ratio
the on theHowever,
fuel. composition of the synthesis
an excessive amount gas for both
of oxygen studied
will biomasses.
completely oxidize,The
leading to the decline of the fuel and the production of syngas.
behavior for both biomasses was similar. Initially, the amount of hydrogen increases, me- Therefore, ER is an
thaneessential
decreases, parameter
due tointhe thefavoring
gasification process [4,12,27,30].
of hydrogen formation Figure 3 shows
reactions, namelythe effect of
reforming
the (7),
of char equivalence
water gas ratio onreaction
shift the composition
(8), andofsteam–methane
the synthesis gasreforming
for both studied
(10). Inbiomasses.
addition to
The behavior for both biomasses was similar. Initially, the amount of hydrogen increases,
the fact that carbon monoxide has a minimal decline, this is also due to the amount of inert
methane decreases, due to the favoring of hydrogen formation reactions, namely reforming
N2 that rises with increasing air intake. However, in the ER close to 0.4, for hardwood
of char (7), water gas shift reaction (8), and steam–methane reforming (10). In addition to
chips,
theand
fact 0.5
thatfor almond
carbon shells,has
monoxide thea minimal
amount decline,
of hydrogen stabilizes
this is also due to and beginsof
the amount toinert
decay
and Nthe formation of carbon dioxide begins. At this ER value, the amount
2 that rises with increasing air intake. However, in the ER close to 0.4, for hardwood chips,
of oxygen pre-
sent and
causes thealmond
0.5 for processshells,
to be the
similar
amountto combustion, with a decrease
of hydrogen stabilizes and beginsin Hto2 and
decayCO andtothe
form
CO2.formation
Thus, theofair intake maximizes gasification in the range of 0.2 to 0.5
carbon dioxide begins. At this ER value, the amount of oxygen present causes of ER, obtaining
the highest
the process H2 values, hightoCO
to be similar composition,
combustion, withand virtually
a decrease in Hzero
2 andCOCO 2 composition.
to form CO2 . Thus,For ER
thebelow
values air intake0.2,maximizes
gasification gasification in the range
is incomplete, of 0.2 to
and above 0.5,0.5gasification
of ER, obtaining the highest
is similar to com-
H2 values,
bustion, with thehighincreased
CO composition,
formation and of
virtually
CO2. zero CO2 composition. For ER values below
0.2, gasification is incomplete, and above 0.5, gasification is similar to combustion, with the
increased formation of CO2 .
70 70
CO CO
H2 H2
60 60
Syngas mole composition (%)
CO2 CO2
50 CH4 50 CH4
N2 N2
40 40
30 30
20 20
10 10
0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Equivalence ratio Equivalence ratio
(a) hardwood chips (b) almond shells

FigureFigure
3. Effect of ERofon
3. Effect ERthe
on composition of syngas
the composition forforhardwood
of syngas hardwoodchips
chips (a)
(a) and almondshells
and almond shells(b).
(b).
3.2.2.3.2.2.
Molar andand
Molar Mass Flow
Mass of of
Flow Syngas
Syngas
Another
Another important
important parameter
parameter totoanalyze
analyzeisis the
the production
production ofofsyngas.
syngas.This
Thisvariable
variable
shows the amount of gas that is produced as a function of time.
shows the amount of gas that is produced as a function of time. Both molar and Both molar and mass
mass
quantities of this production were studied as a function of the equivalence
quantities of this production were studied as a function of the equivalence ratio. As ratio. As thethe
independent variable is the air intake, the flows were also analyzed in a N2 –free basis.
independent variable is the air intake, the flows were also analyzed in a N 2–free basis.
Therefore, Figure 4 shows the behavior of the molar and mass flow as a function of the
Therefore, Figure 4 shows the behavior of the molar and mass flow as a function
equivalence ratio for both studied biomasses. It is observed that the mass flow rate increases
of the
equivalence ratiooffor
with the rise both studied
air intake. biomasses.
This is expected It is observed
because that theofmass
a greater amount flow rate
air promotes thein-
creases with the rise of air intake. This is expected because a greater amount
formation of H2 and, for ER values higher than 0.4, the formation of CO2 , in addition of air pro-
motes the formation of H and, for ER values higher than 0.4, the formation
to increasing the amount of the inert gas N2 . When N2 is not considered in the mass
2 of CO 2, in
addition
flow, to increasing
there the amount
is a reduction of the inert
of approximately 1%gas N2. ER
at low When N2 is
values andnot considered in
approximately 6%the
at high ER values. The molar flow increases until approximately an ER value of 0.4, for
hardwood chips, and 0.5 for almond shells, after which the molar flow decreases. This can
be explained by the fact that from this equivalence ratio there is a decline in the amount of
H2 and a rise in CO2 . As the molar mass of CO2 is greater than the molar mass of H2 , a
mass flow, there is a reduction of approximately 1% at low ER values and approximately
6% at high ER values. The molar flow increases until approximately an ER value of 0.4,
for hardwood chips, and 0.5 for almond shells, after which the molar flow decreases. This
can be explained by the fact that from this equivalence ratio there is a decline in the
ChemEngineering 2021, 5, 20 amount of H2 and a rise in CO2. As the molar mass of CO2 is greater than the molar 12 of 24
mass
of H2, a greater mass of CO2 gas is required to obtain the same molar amount of H2. This
behavior is observed in the curves at the moment when H2 starts to decline and CO2 in-
creases, which
greater mass is
of where
CO2 gasthe molar flow
is required of thethe
to obtain synthesis gas amount
same molar starts toofdecrease. When N2 is
H2 . This behavior
removed from in
is observed thethe
molar flow,
curves there
at the is a fallwhen
moment in theHproduction of syngas
2 starts to decline and by
COapproximately
2 increases,
1%which
at lowisER
where the molar
values, flow
and 4% atofhigh
the synthesis
ER values. gas starts to decrease. When N2 is removed
from the molar flow, there is a fall in the production of syngas by approximately 1% at low
ER values, and 4% at high ER values.
0.38 7.0 0.38 7.0
6.8 6.8
0.36 0.36
Syngas molar flow (kmol/h)

6.6 6.6
Syngas mass flow (kg/h)

0.34 0.34
6.4 6.4
0.32 6.2 0.32 6.2
0.30 6.0 0.30 6.0
5.8 5.8
0.28 Molar flow 0.28 Molar flow
Molar flow without N2 5.6 Molar flow without N2 5.6
0.26 Mass flow 0.26 Mass flow
5.4 5.4
Mass flow without N2 Mass flow without N2
0.24 5.2 0.24 5.2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure 4. Effect
Figure of ER
4. Effect of on
ERthe molar
on the and
molar mass
and flow
mass flowofofsyngas
syngasobtained withhardwood
obtained with hardwoodchips
chips(a)(a)
andand almond
almond shells
shells (b). (b).
3.2.3. Heating
3.2.3. Value
Heating Value
The heating
The heatingvalue
value of aaproduct
product gasgas
is aismeasure
a measure of quality.
of quality. This value
This heating heating value de-
decreases
as more
creases air is supplied
as more [20,31]. [20,31].
air is supplied Figure 5Figure
shows 5the behavior
shows the of the highofand
behavior thelow heating
high and low
values due to the growth in the equivalence ratio for both studied biomasses.
heating values due to the growth in the equivalence ratio for both studied biomasses. As As predicted,
both heating
predicted, both values
heating decline
valueswith increasing
decline ER (approximately
with increasing 33% for hardwood
ER (approximately 33% for and
hard-
wood and 30% for almond shell). This is due to the fact that the increase of air ina the
30% for almond shell). This is due to the fact that the increase of air in the process causes
greater amount of N2 in the synthesis gas, in addition to favoring the formation of CO2 . If
process
ChemEngineering 2021, 5, x FOR PEER REVIEW causes a greater amount of N2 in the synthesis gas, in addition to favoring13the of 24
N2 is removed from the synthesis gas, there is a rise in the heating value (approximately
formation of CO 2. If N2 is removed from the synthesis gas, there is a rise in the heating
5% for hardwood and 6% for almond shell). However, the same decreasing behavior is
value (approximately
observed when the ER5% for hardwood
is varied. Therefore, and
the 6%
CO2for almond
upsurge shell).
is the factorHowever, the same
that most affects
decreasing behavior
the calorific is observed
value. Thus, when
the heating the ER
value is varied.
of the Therefore,
gas declines with thethe CO2 upsurge
increase in ER. is the
factor that most affects the calorific value. Thus, the heating value of the gas declines with
21 the increase in ER. 21
HHV HHV
20 HHV without N2 20 HHV without N2
19 LHV 19 LHV
LHV without N2 LHV without N2
Heating value (MJ/kg)
18 18
17 17
16 16
15 15
14 14
13 13
12 12
11 11
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure 5. Effects
Figure of ER
5. Effects onon
of ER heating
heatingvalues
valuesof
ofthe
the synthesis gasobtained
synthesis gas obtainedwith
with hardwood
hardwood chips
chips (a) and
(a) and almond
almond shellsshells
(b). (b).
3.2.4. Gasifier Temperature

Usually, the gasification temperature is analyzed as an independent variable depend-
ing on the composition of the synthesis gas [6,18]. However, it is interesting to analyze the
Figure 5. Effects of ER on heating values of the synthesis gas obtained with hardwood chips (a) and almond shells (b).
ChemEngineering 2021, 5, 20 3.2.4. Gasifier Temperature 13 of 24
Usually, the gasification temperature is analyzed as an independent variable depend-

ing on the composition of the synthesis gas [6,18]. However, it is interesting to analyze the
temperature
3.2.4. Gasifierbehavior
Temperature of the gasifier when considering the temperature as a dependent
variable. Figure 6 shows
Usually, the gasification how the temperature
temperature is analyzedin the
as anreactors behave
independent with the
variable growth in
depend-
the
ingequivalence ratio for
on the composition the synthesis
of the two biomasses analyzed.
gas [6,18]. However, It can
it is be noted that
interesting up to the
to analyze the ER of
0.4, for hardwood
temperature behavior chips, and
of the 0.45 for
gasifier almond
when shells,the
considering thetemperature
temperature asof the gasification
a dependent
variable.with
declines Figurethe6 increase
shows how the temperature
of air. in the expected
It is the behavior reactors behave with the growth
in gasification in main
since the
the equivalence ratio for the two biomasses analyzed. It can be
reduction reactions are endothermic—Boudouard (6), reforming of char (7), steam–me- noted that up to the ER of
0.4, for hardwood chips, and 0.45 for almond shells, the temperature
thane reforming (10), consuming the existing heat and causing the temperature to de- of the gasification
declines with the increase of air. It is the behavior expected in gasification since the main
crease. From that value (0.4 or 0.45), the temperature starts to increase. This is due to the
reduction reactions are endothermic—Boudouard (6), reforming of char (7), steam–methane
fact that from that ER value, gasification is similar to combustion. Thus, the equilibrium
reforming (10), consuming the existing heat and causing the temperature to decrease. From
ofthat
thevalue
hydrogen
(0.4 oroxidation
0.45), thereaction
temperature shiftsstarts
to form more water,
to increase. This causing
is due tothe thewater gas shift
fact that
reaction
from that ER value, gasification is similar to combustion. Thus, the equilibrium of the to be
(8) gasification reaction to shift to the formation of CO 2 , causing energy
released,
hydrogenand thereby
oxidation increasing
reaction shifts the temperature
to form more water, inside the the
causing reactor.
waterItgas is important to high-
shift reaction
light that in this
(8) gasification ER there
reaction is no
to shift to longer CH4, so
the formation of there is no favoring
CO2 , causing energy to ofbe
the steam–methane
released, and
thereby increasing
reforming the temperature
(10) reaction, inside the reactor. It is important to highlight that in
which is endothermic.
this ER there is no longer CH4 , so there is no favoring of the steam–methane reforming (10)
reaction, which is endothermic.
1350 1350
1300 1300
1250 1250
Gasifier temperature (°C)
1200 1200
1150 1150
1100 1100
1050 1050
1000 1000
950 950
900 900
850 850
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure 6. Effect
Figure ofofER
6. Effect ERon
onthe
thetemperature of the
temperature of thegasifier
gasifieroperated
operated with
with hardwood
hardwood chips
chips (a) almond
(a) and and almond
shellsshells
(b). (b).
3.3. Effect of Steam to Biomass Ratio

The study of the influence of steam input on the composition of syngas, heating
value, and gasification temperature was done considering SBR as the independent variable,
with the molar composition of syngas, flow of syngas, heating value, and gasification
temperature as dependent variables. For this study, the biomass input is fixed at 5 kg/h. In
addition, the steam intake was varied up to 3.6 kg/h (approximately 0.7 SBR) and the air
intake was fixed at 1.25 kg/h (approximately 0.4 ER).
3.3.1. Molar Composition of Syngas

The steam to biomass ratio is the ratio of the flow of steam to the flow of biomass. This
is an important parameter in the gasification process as it is directly linked to the formation
of H2 . The steam upsurge in the reactor favors H2 formation reactions, especially water
gas shift reaction (8) and steam–methane reforming (10). However, it also ends up favoring
the formation of CO2 . Thus, it is necessary to define the best ratio to not have unwanted
amounts of CO2 in the synthesis gas [17,23,32]. Figure 7 shows the behavior of the syngas
composition as the steam to biomass ratio increases. Both biomasses revealed similar
behavior. So, the rise in steam causes the amount of carbon monoxide and methane to
formation of H2. The steam upsurge in the reactor favors H2 formation reactions, especially
water gas shift reaction (8) and steam–methane reforming (10). However, it also ends up
favoring the formation of CO2. Thus, it is necessary to define the best ratio to not have
unwanted amounts of CO2 in the synthesis gas [17,23,32]. Figure 7 shows the behavior of
ChemEngineering 2021, 5, 20 the syngas composition as the steam to biomass ratio increases. Both biomasses revealed14 of 24
similar behavior. So, the rise in steam causes the amount of carbon monoxide and methane
to decrease. Hydrogen and carbon dioxide, on the other hand, exhibit the opposite behav-
ior, increasing the composition with increasing steam. This is due to the fact that steam
decrease. Hydrogen and carbon dioxide, on the other hand, exhibit the opposite behavior,
favors the water gas shift reaction (8) and steam–methane reforming (10) reactions, con-
increasing the composition with increasing steam. This is due to the fact that steam favors
suming CO and CH4 and forming mostly H2 and CO2.
the water gas shift reaction (8) and steam–methane reforming (10) reactions, consuming
CO and CH4 and forming mostly H2 and CO2 .
60 60
CO CO
H2 H2
50 CO2 50 CO2

CH4 CH4
40 40
30 30
20 20
10 10
0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Steam to biomass ratio Steam to biomass ratio

Figure
Figure7.7.Effect
EffectofofSBR
SBRononthe
thecomposition
compositionofofsyngas
syngasfor
forhardwood
hardwoodchips
chips(a)
(a)and
andalmond
almondshells
shells(b).
(b).
3.3.2.
3.3.2.Molar
Molarand andMassMassFlow
FlowofofSyngas
Syngas
ItItisisalso
also important to analyzethe
important to analyze theproduction
productionofofsyngas
syngasininrelation
relationtotothe
thefeeding
feedingofof
steam
steam into the gasifier. Thus, the influence of steam on the molar and mass amountofof
into the gasifier. Thus, the influence of steam on the molar and mass amount
syngas
syngasflow flow waswas studied.
studied. Figure
Figure8 shows
8 showsthe behavior of theofmolar
the behavior and mass
the molar flow of
and mass syn-of
flow
gas
syngas as a function of the steam to biomass ratio for the two studied biomasses. that
as a function of the steam to biomass ratio for the two studied biomasses. Note Note
both
thatmass
both andmassmolar production
and molar of syngas
production increase
of syngas with increasing
increase SBR. SBR.
with increasing This can
Thisbecanex-be
plained
explained by the
by thefactfact
thatthat
thethe
surge
surgein steam
in steampromotes
promotes thetheformation
formationofofHH2 and CO2 mainly
2 and CO2 mainly
because
ChemEngineering 2021, 5, x FOR PEER because of the water gas shift reaction (8). This causes the mass productiontotoincrease
REVIEW of the water gas shift reaction (8). This causes the mass production increase
15 of 24
with
with the growth of the SBR. Regarding molar production, the increasing behavior canbebe
the growth of the SBR. Regarding molar production, the increasing behavior can
explained
explainedby bythe thefact
factthat
thatregardless
regardlessofofthetheSBR
SBRvalue
valueanalyzed,
analyzed,the theamount
amountof ofHH22and
andCO CO2 2
isisalways increasing,
always increasing, with
with no change in the behavior of the molar composition of syngas
composition (as seen in theno
ERchange
study),inmaking
the behavior
also theofproduction
the molar composition
of syngas toof syngas
perform
(CO
(COand andHH 2), ),
2 that
that are
are always
always increasing,
increasing, without
without increasing
increasing and
and then
then decreasing
decreasing ininHH2 2
in a similar way.
composition (as seen in the ER study), making also the production of syngas to perform in
a similar way.
0.48 8.0 0.48 8.0
7.8 7.8
0.46 0.46
7.6 7.6
0.44 0.44
7.4 7.4
0.42 7.2 0.42 7.2
0.40 7.0 0.40 7.0
6.8 6.8
0.38 0.38
6.6 6.6
0.36 Molar flow 6.4
0.36 Molar flow 6.4
Mass flow Mass flow
0.34 6.2 0.34 6.2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure
Figure8.8.Effect
EffectofofSBR
SBRon
onthe
themolar
molarand
andmass
massflow
flowof
ofsyngas
syngasobtained
obtainedwith
withhardwood
hardwoodchips
chips(a)
(a)and
and almond
almond shells
shells (b).
(b).
3.3.3. Heating Value

The heating value of the synthesis gas decreases with the rise of steam in the gasifi-
cation process [17,33]. As can be observed in Figure 9, the behavior for both biomasses
was similar to that found in the literature. As the steam increases, the calorific value de-
0.34 6.2 0.34 6.2
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure 8. Effect of SBR on the molar and mass flow of syngas obtained with hardwood chips (a) and almond shells (b).
3.3.3. Heating Value

3.3.3. The
Heating Value
heating value of the synthesis gas decreases with the rise of steam in the gasifi-
cation
Theprocess
heating[17,33].
value of Asthe
can be observed
synthesis in Figurewith
gas decreases 9, the
thebehavior for both
rise of steam in thebiomasses
gasifica-
wasprocess
tion similar [17,33].
to that found
As canin bethe literature.
observed As the9,steam
in Figure increases,
the behavior forthe
bothcalorific
biomassesvalue de-
was
similar to that found in
cline (approximately 21%thefor
literature.
hardwood Asand
the 20%
steam forincreases, the calorific
almond shell). This is value
due todecline
the fact
(approximately 21% forof
that a higher amount hardwood and 20%
steam provides a for almond
higher amountshell).
of This
CO2 isanddue to the fact
a lower that aof
amount
higher amount of steam provides a higher amount
CO in the syngas. Even with the rise in the amount of H of CO and a lower amount of
2 2, this decay of CO makes the CO in
the syngas. Even with the rise in the amount
internal enthalpy released by the syngas to be lower. of H 2 , this decay of CO makes the internal
The calorific value is defined as the
enthalpy
amount released
of energybyproduced
the syngas bytothebefuel
lower. Theitcalorific
when burns. Thevalue COis defined
oxidation as reaction
the amount of
is exo-
energy
thermic,produced
so there by
is athe fuelamount
lower when it of burns.
CO inThetheCO oxidation
syngas, whichreaction
causes istheexothermic, so
calorific value
there is a lower
to decrease. amount of
Therefore, CO ininthe
a drop COsyngas,
and awhich
rise incauses the calorific
CO2 causes value tovalue,
the calorific decrease.
both
Therefore, a drop in CO and
higher and lower, to be lower. a rise in CO 2 causes the calorific value, both higher and lower,
to be lower.
HHV HHV
18 LHV 18 LHV
17 17

16 16
15 15
14 14
13 13
12 12
11 11
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure9.9.Effects
Figure EffectsofofSBR
SBRon
onheating
heatingvalues
valuesofofthe
thesynthesis
synthesisgas
gasobtained
obtainedwith
withhardwood
hardwoodchips
chips(a)
(a)and
andalmond
almondshells
shells(b).
(b).
3.3.4. Gasifier Temperature

Analyzing the behavior of temperature as a dependent variable with the growth in
the amount of steam in the reactors, it is observed that the increase of the steam to biomass
ratio leads to a decrease of the gasification temperature [34], as evidenced in Figure 10 for
the two biomasses. This is due to the fact that the rise in water favors the formation of
H2 . The water gas shift reforming reaction (8) is exothermic, however, the steam–methane
reforming reaction (10) is endothermic, with five times the enthalpy. In addition, as the
steam enters at 100 ◦ C, the reaction temperature is expected to diminish. In this way, the
expected behavior that is observed is the reduction of the temperature with the upsurge of
steam entering the reactor.
3.4. Effect of the Temperature of the Gasifier

The analysis of the influence of the gasification temperature on the molar composition
and the heating value of the syngas was carried out with the gasification temperature as an
independent variable, and with the composition of syngas, flow of syngas, and heating
value as dependent variables. For this study, a biomass input of 5 kg/h is fixed. In addition,
the gasification temperature was varied from 600 to 1200 ◦ C, the air intake was fixed at
1.25 kg/h (approximately 0.4 ER) and there was no vapor inlet, so only the water present
in the biomass moisture was used.
The water gas shift reforming reaction (8) is exothermic, however, the steam–methane re-
forming reaction (10) is endothermic, with five times the enthalpy. In addition, as the
steam enters at 100 °C, the reaction temperature is expected to diminish. In this way, the
expected behavior that is observed is the reduction of the temperature with the upsurge
ChemEngineering 2021, 5, 20 of steam entering the reactor. 16 of 24
860 860
840 840
820 820

800 800
780 780
760 760
740 740
720 720
700 700
680 680
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Figure
Figure10.
10.Effect
EffectofofSBR
SBRon
on the
the temperature ofthe
temperature of thegasifier
gasifieroperated
operatedwith
with hardwood
hardwood chips
chips (a) (a)
andand almond
almond shells
shells (b). (b).
3.4. Effect
3.4.1. Molarof the Temperature
Composition of of the Gasifier
Syngas
The analysis of temperature
The gasification the influence of the gasification
is another temperature
important parameter onsyngas
in the the molar composi-
production
tion and Hydrogen
process. the heatingisvalue of the
expected syngas was
to increase withcarried out with temperature,
the gasification the gasification temperature
reaching the
as an independent
maximum, and then variable,
graduallyand with the
decrease atcomposition of syngas,
higher temperatures. flow of syngas,
Gasification and heat-
is generally
satisfactory ◦ C [12,27,33]. Figure 11 shows the behavior of the
ing value asatdependent
a temperature of 800For
variables. this study, a biomass input of 5 kg/h is fixed. In
addition, the gasification temperature wasthe
molar composition of the synthesis gas with growth
varied in the
from 600gasifier
to 1200temperature
°C, the air for bothwas
intake
biomasses. While CO increases, H rises to a maximum and then declines
fixed at 1.25 kg/h (approximately 20.4 ER) and there was no vapor inlet, so only the water with growing
temperature.
present in theCO 2 and CH
biomass 4 decrease.
moisture wasThis is due to the fact that the reactions of Boudouard
used.
(6), reforming char (7) and steam–methane reforming (10) are endothermic. Thus, with
increasing
3.4.1. Molartemperature,
Compositionthe of balance
Syngas shifts to the formation of products, leading to the
consumption of more CO2 and CH4 and to the production of more CO. The reactions of
waterThegasgasification
shift reactiontemperature is another important
(8) and hydrogasification parameter
(9) are exothermic, so a in the syngas
higher produc-
temperature
tion process. Hydrogen is expected to increase with the gasification temperature,
makes the reaction more difficult and the production of less CO2 , H2, and CH4 . Hydrogen reaching
the maximum,
fluctuation and
can be then gradually
caused decrease
by the combined at higher
effects temperatures.
of reactions Gasification
in the gasification zone.isThe
gener-
ally satisfactory at a temperature of 800 °C [12,27,33]. Figure 11 shows
water gas shift reaction (8) is one of the most important for the final composition of the the behavior of the
molar
synthesiscomposition
gas due toof thethe synthesis
ability gaswith
to react withCO the
andgrowth
H2 O andin the gasifier
to form CO2temperature
and H2 . At for
lowerbiomasses.
both temperatures, the CO
While water gas shift H
increases, reaction (8)aprevailed
2 rises to maximum in the
andproduction
then declinesof Hwith
2 , while
grow-
at higher
ing temperatures
temperature. the action
CO2 and was impaired.
CH4 decrease. The
This is dueother twofact
to the reactions
that thefor reactions
the formation
of Bou-
of H2 reforming
douard char (7)
(6), reforming charand(7)steam–methane
and steam–methane reforming (10) are
reforming endothermic
(10) and may
are endothermic. Thus,
contribute to the increase. However, after the temperature of 800 ◦ C, the reactions may be
with increasing temperature, the balance shifts to the formation of products, leading to
limited
the due to the of
consumption lack of reagents
more CO2 and such
CHas4 and
CH4 toand H2production
the O. Thus, theofcombined
more CO. effects
The of the
reactions
reactions 7, 8, 9, and 10 can cause a reduction in hydrogen after 800 ◦ C.
of water gas shift reaction (8) and hydrogasification (9) are exothermic, so a higher tem-
perature makes the reaction more difficult and the production of less CO2, H2, and CH4.
Hydrogen fluctuation can be caused by the combined effects of reactions in the gasifica-
of H2, while at higher temperatures the action was impaired. The other two reactions for
the formation of H2 reforming char (7) and steam–methane reforming (10) are endother-
mic and may contribute to the increase. However, after the temperature of 800 °C, the
reactions may be limited due to the lack of reagents such as CH4 and H2O. Thus, the com-
ChemEngineering 2021, 5, 20 bined effects of the reactions 7, 8, 9, and 10 can cause a reduction in hydrogen after 800 °C.
17 of 24
58 58
CO CO
56 H2 56 H2

54 54
52 52
50 50
48 48
46 46
44 44
42 42
40 40
38 38
36 36
600 700 800 900 1000 1100 1200 600 700 800 900 1000 1100 1200
Gasifier temperature (°C) Gasifier temperature (°C)
CO2 CO2
7 CH4 7 CH4
6 6

5 5
4 4
3 3
2 2
1 1
0 0
600 700 800 900 1000 1100 1200 600 700 800 900 1000 1100 1200

FigureFigure
11. Effects of theof
11. Effects gasifier temperature
the gasifier on the
temperature composition
on the ofof
composition syngas
syngasproduced
producedfrom
from hardwood chips(a)
hardwood chips (a)and
and almond
almond
shells (b).
shells (b).
3.4.2.3.4.2. Heating
Heating Value
Value
The The heating value tends to rise with increasing temperature in the gasifier since a
heating value tends to rise with increasing temperature in the gasifier since a
surge in the composition of H2 and CO in the synthesis gas is expected [17,34]. Figure 12
surge in the composition of H2 and CO in the synthesis gas is expected [17,34]. Figure 12
shows the behavior of the heating value when the temperature is varied for both biomasses.
showsIt isthe behavior
noticeable the of
risethe heating
in the heating value
valuewhen theincrease
with the temperature is varied temperature
in the gasification for both bio-
masses. It is noticeable the rise in the heating value with the increase
(approximately 4% for hardwood and 3% for almond shell). This is due to the fact in the gasification
that a
temperature
growth in(approximately
temperature favors 4%theforformation
hardwood of Hand
2 and 3%CO for
in almond
the syngas,shell).
rising This
the is due to
calorific
the fact
value.that a growth
Even with thein temperature
stabilization andfavors the formation
slight decrease of H2after
of hydrogen andtheCO in the syngas,
temperature of
◦
rising
800theC,calorific
the CO value.
continuesEven with theand
to increase stabilization and slight
a higher amount of CO decrease of hydrogen
in the syngas after
causes the
energy released
the temperature by the
of 800 °C,syngas
the COtocontinues
be higher,to
thus the growth
increase and aofhigher
CO tends to augment
amount of CO inthethe
heating
syngas causesvalue.
the energy released by the syngas to be higher, thus the growth of CO tends
to augment the heating value.
ChemEngineering2021,
ChemEngineering 2021,5,5,x20
FOR PEER REVIEW 1818ofof2424
HHV
HHV
15.2 LHV 15.2
15.2 LHV 15.2
14.8 14.8 14.8

14.8


14.4 14.4 14.4 14.4
14.0 14.0 14.0 14.0
13.6 13.6
13.6 13.6 HHV HHV
LHV
LHV
13.2 13.2
13.2 13.2
12.8 12.8
12.8 12.8
12.4 12.4
12.4 600 700 800 900 1000 1100 1200 600
12.4 700 800 900 1000 1100 1200
600 700 800
Gasifier 900 1000(°C) 1100
temperature 1200 600 700 temperature
Gasifier 800 900
(°C) 1000 1100 1200

Figure 12. Effect of the gasifier temperature on heating values of the synthesis gas obtained with hardwood chips (a) and
almond
Figure
Figure shells
12. Effect
12. (b).
of the
Effect gasifier
of the temperature
gasifier temperatureon
on heating valuesofofthe
heating values thesynthesis
synthesis
gasgas obtained
obtained withwith hardwood
hardwood chips chips
(a) and(a) and
almond shells
almond (b).(b).
shells
3.5. Combined Effect of Equivalence Ratio and Steam to Biomass Ratio
3.5.
3.5. The combined
Combined
Combined Effectindependent
Effect of Equivalencevariables
of Equivalence Ratioand
Ratio equivalence
and Steam
Steam ratioRatio
andRatio
to Biomass
to Biomass steam to biomass ratio
were used to analyze the behavior of the composition of syngas, flow of syngas, and the
TheThecombined
combined independent variables
independent variables equivalence
equivalence ratio
ratio andandsteamsteam to biomass
to biomass ratio ratio
gasification temperature, aiming to find maximum and minimum parameters of these in-
were used to analyze the behavior of the composition of syngas, flow of syngas,the
were used to analyze the behavior of the composition of syngas, flow of syngas, and and the
dependent variables in
gasificationtemperature, order
temperature, aimingto obtain
aiming to a
findsynthesis
maximum gas rich
and in CO
minimum and H 2. The air intake
parameters of these
gasification
was varied up variables
to 2.4 kg/h to find maximum and minimum parameters of these in-
independent in(approximately
order to obtain0.8 ER), the feed
a synthesis gas of steam
rich in COup and
to 3.6
H2kg/h
. The(ap-
air
dependent
proximately variables
0.7 SBR), in order to obtain a synthesis gas rich5in CO and H2. The air intake
intake was varied up and the
to 2.4 biomass
kg/h intake remained
(approximately fixed
0.8 ER), the at
feedkg/h.
of steam up to 3.6 kg/h
was varied up to 2.4 kg/h (approximately 0.8 ER), the feed of steam up to 3.6 kg/h (ap-
(approximately 0.7 SBR), and the biomass intake remained fixed at 5 kg/h.
proximately
3.5.1. Carbon0.7 SBR), and the biomass intake remained fixed at 5 kg/h.
Monoxide
3.5.1.
TheCarbon
previousMonoxide
analysis of ER and SBR showed that both the increase in air and in
3.5.1.
steamCarbon
led to
The aMonoxide
decrease
previous in theof
analysis composition
ER and SBR of showed
CO in the syngas.
that both Figure 13 shows
the increase how
in air andthein
combination
steam led toof
a these
decrease twoin parameters
the influences
composition of CO the
in composition
the syngas.
The previous analysis of ER and SBR showed that both the increase in air of carbon
Figure 13 monoxide
shows how in and in
the
the gas obtained
combination
steam led to a of at the end
these two
decrease of the process
in parameters for the
influences
the composition two
of CO biomasses
the in compositionstudied.
the syngas. As
of Figure expected,
carbon 13
monoxide the
shows how in the
combined rise of ERatand
the gas obtained theSBR
endreduces the composition
of the process for the two in CO due to favoring
biomasses studied.the
Asformation
expected,
combination of these two parameters influences the composition of carbon monoxide in
ofthe
H2combined
and CO2. Itriseis necessary
of ER andtoSBR analyze the other
reduces compositionsintoCO
the composition finddue
theto
best combina-
favoring the
the
tion
gas obtained
of ER and
formation of H SBR,
at the end of theobserved
however,
processto
CO2 . It itisisnecessary
for
that
the two
these values
biomasses
must
studied. As find
expected,
be up to 0.5to(ER) and
the
2 and analyze the other compositions the
combined
best
0.2 rise
combination
(SBR), of ER and SBR
of ER and SBR,
because combinations reduces the
however,
with composition
values it is observed
greater in CO due
that these
than these to favoring
values must
considerably the
be up
decrease formation
theto
ofcomposition
H2(ER)
0.5 and and
COof20.2
. CO
It(SBR),
isinnecessary
because
the syngas. to analyze thewith
combinations other compositions
values greater than tothese
find considerably
the best combina-
tion of ER the
decrease andcomposition
SBR, however, of COitinistheobserved
syngas. that these values must be up to 0.5 (ER) and
0.2 (SBR), because combinations with values greater than these considerably decrease the
CO mole composition (%) CO mole composition (%)
composition of CO in the syngas.
61.20 58.50
56.25 53.98
0.6 0.6
Steam to biomass ratio
51.30 49.45
CO mole composition (%) CO mole composition (%)

46.35 44.92
61.20 58.50
0.4 0.4
41.40 40.40
56.25 53.98
0.6 0.6
36.45 35.88
51.30 49.45
0.2 31.50 0.2 31.35
46.35 44.92
0.4 26.55 0.4 26.83
41.40 40.40
21.60 22.30
0.0 0.0
0.2 0.4 0.6 36.45 0.2 0.4 0.6 35.88
0.2 31.50 0.2 31.35
26.55 26.83
21.60 22.30
0.0 0.0
Figure
Figure13.
13. Combined
0.2 Combined 0.4 effects of
of ER
effects0.6 and SBR
ER and SBR on
on the
thecomposition
compositionofofCO
COininthe
thesyngas
syngas produced
0.2produced with
0.4 with hardwood
hardwood
0.6 chips
chips (a)
(a) and
and almond shells (b).
Equivalence
almond shells (b). ratio Equivalence ratio

Figure 13. Combined effects of ER and SBR on the composition of CO in the syngas produced with hardwood chips (a)
3.5.2. Hydrogen
The previous ER study showed that the increase in air first increases the amount of
3.5.2. Hydrogen
H2 and after values of 0.4 and 0.5 (for hardwood chips and almond shells, respectively)
The previous
that amount decreases. ER study showed
The SBR that the
analysis increase
showed inthe
that air first increases
increase the amount
of steam of
feed favors
H2 and after values of 0.4 and 0.5 (for hardwood chips and almond shells, respectively)
the composition of H2 in the syngas. Figure 14 shows how the combination of these two
that amount decreases. The SBR analysis showed that the increase of steam feed favors
parameters affects the composition of H2 for both biomasses. It is observed that the in-
the composition of H2 in the syngas. Figure 14 shows how the combination of these two
crease of ER up to 0.4 (in Figure 14a) and 0.5 (in Figure 14b) causes the composition of H2
parameters affects the composition of H2 for both biomasses. It is observed that the increase
toofgrow,
ER updecreasing after 14a)
to 0.4 (in Figure thatand
value. The
0.5 (in upsurge
Figure in steam
14b) causes the favors the formation
composition of H2,
of H2 to grow,
obtaining
decreasing compositions higher
after that value. Thethan 50%.inItsteam
upsurge is observed thatformation
favors the the best values to obtain a
of H2 , obtaining
syngas rich in H is with ER between 0.3 and 0.5 because the lack of air
compositions higher than 50%. It is observed that the best values to obtain a syngas rich
2 or the excess causes
in
a decline in H . The feed of steam favors the formation of H , but it
H2 is with ER between 0.3 and 0.5 because the lack of air or the excess causes a decline in
2 2 also favors the for-
mation of feed
H2 . The CO2 ofand decreases
steam favors the
the composition
formation of H of2 ,CO.
but Therefore,
it also favors it is
thenecessary
formationtoofanalyze
CO2
the
andcomposition
decreases the of composition
CO2 to choose the best
of CO. SBR input
Therefore, parameter.
it is necessary to analyze the composition
of CO2 to choose the best SBR input parameter.
H2 mole composition (%) H2 mole composition (%)

51.70 53.10
47.51 48.71
0.6 0.6

43.33 44.33
39.14 39.94
0.4 0.4
34.95 35.55
30.76 31.16
0.2 26.57 0.2 26.77
22.39 22.39
18.20 18.00
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6

Figure 14.14.
Figure Combined
Combined effects ofof
effects ERERand
andSBR
SBRon
onthe
thecomposition
composition of H22 in
in the syngas producedwith
syngas produced withhardwood
hardwood chips
chips (a)(a)
andand
almond shells
almond (b).(b).
shells
3.5.3. Carbon Dioxide

3.5.3. Carbon Dioxide
From the previous ER and SBR analyzes, it can be observed that the increase of both
From the previous ER and SBR analyzes, it can be observed that the increase of both
air and steam favor the formation of CO2. Figure 15 shows the behavior of the CO2 com-
air and steam favor the formation of CO2 . Figure 15 shows the behavior of the CO2
position in the synthesis gas when these two parameters are combined. It is observed that
composition in the synthesis gas when these two parameters are combined. It is observed
larger ER and
that larger ERSBR
andvalues lead lead
SBR values to higher amounts
to higher amountsof CO in the
of 2CO syngas. Therefore, the best
2 in the syngas. Therefore, the
range
best for working
range with air
for working withand
airsteam is upistoup0.5
and steam tofor
0.5 ER
for and 0.2 0.2
ER and for for
SBR.
SBR.
3.5.4. Molar and Mass Flow of Syngas

The previous ER study showed that the increase of air first increases the molar flow
of syngas and that after 0.4 and 0.5 (for hardwood chips and almond shell, respectively)
the flow decreases. Regarding the mass flow, there is a rise in value, regardless of the ER.
The analysis of the SBR effect showed that the increase in steam favors the molar and mass
flows. Figure 16 shows how the combination of these two parameters interferes in the
molar and mass production of syngas for both biomasses. It is observed that the increase
of ER up to 0.4 for hardwood chips and 0.5 for almond shells, causes the molar flow to
increase, decreasing after that value. The upsurge in steam favors the molar production
of syngas. Note that the best values for higher molar flow occur between 0.3 and 0.5 due
to the fact that the lack of air or the excess causes the amount of H2 to decline and conse-
quently the molar flow as well. The feeding of steam favors the molar production of syn-
ChemEngineering 2021,
ChemEngineering 5, x5,FOR
2021,
gas. However, the growth in SBR, in addition to increasing the composition of20Hof2,20
20 PEER REVIEW
in-
24 of 24
creases the composition of CO2.
quentlyCOthe molar
mole
2
flow(%)as well. The feeding of steam favors the molar
composition production
CO mole composition (%)of syn- 2
gas. However, the growth in SBR, in addition to increasing the composition

24.20 21.30 of H2, in-
0.6
creases the composition
21.18 of CO2. 0.6
18.64

18.15 15.98
15.13 13.31
CO2 mole composition (%) CO2 mole composition (%)
0.4 0.4
24.20
12.10 10.6521.30
21.18
9.075 7.98818.64
0.6 0.6
0.2 0.2

6.050
18.15 5.32515.98
3.025
15.13 2.66313.31
0.4 0.4
0.000
12.10 0.00010.65
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6
9.075 7.988
0.2 6.050 0.2 5.325
(a) hardwood chips 3.025 (b) almond shells 2.663
Figure
0.0 15. 15.
Figure Combined
Combined effects of of
effects ERER
and SBR
and ononthe
SBR composition
0.000
the compositionof
ofCO in
in the
CO220.0 the syngas produced with
syngas produced withhardwood
hardwoodchips
chips0.000
(a)(a)
0.2 0.4 0.6 0.2 0.4 0.6
andand
almond shells
almond (b).(b).
shells
3.5.4.
It isMolar and Massthat
also observed Flow ofincrease
the Syngas of both ER and SBR rises the mass flow of syngas.
(a) hardwood chips
As observed in the molar
The previous ER study showed flows, afterthat
ER thevalues (b)
of 0.4
increase ofalmond
and shells thechips
0.5 increases
air first (hardwood molarand flowal-
mond
Figure 15. Combined effects of ER
of shells,
syngas
and SBRandrespectively)
that
on theafter there
0.4 andis
composition a (for
0.5
of decrease
in theinsyngas
CO2hardwood thechips
molar andflow
produced caused
almond
with by respectively)
shell,
hardwood the chips
decline (a) of
and almond shells (b). H2the
andflowthe decreases.
increase inRegarding
SBR favors thethe
masscomposition
flow, there of is aHrise
2, but also increases
in value, regardless theofcomposi-
the ER.
The
tion ofanalysis
CO2. Thus, of thealthough
SBR effectthe showed
ER and thatSBRthe increase
increase inthesteam
massfavors
flow the molar and
of syngas, thismassflow
flows.
may not Figure
It ishave
also the 16 shows how
best compositions
observed the combination
of H2 of
that the increase and of
CO.ER
both these two
Therefore,
and SBRin parameters
relation
rises interferes
to the
the mass in
production
flow the
of syngas.
Asmolar
of syngas, and
observed mass
it is in production
recommended
the of
molar flows,to syngas
work for
with
after ERboth
ER biomasses.
values
values It is 0.5
of between
0.4 and observed that
0.3 (hardwood
and 0.5 andthechips
increase
low SBR.
and al-
of ER up to 0.4 for hardwood chips and 0.5 for almond shells, causes the molar flow to
mond shells, respectively) there is a decrease in the molar flow caused by the decline of
increase, decreasing after that value. The upsurge in steam favors the molar production
H2 and the increase in SBR favors the composition of H2, but also increases the composi-
of syngas. Note that the best values for higher molar flow occur between
Molar flow (kmol/h)
0.3 and 0.5
tion
dueoftoCO the2. fact
Thus, that although the ER and SBR increase the mass flowMolar
0.4430the lack of air or the excess causes the amount of H2 to decline
of flow (kmol/h)
syngas,
0.4670
this
andflow
may not have the
consequently the0.4193 best compositions of H 2 and CO. Therefore, in relation to the production
molar flow as well. The feeding of steam favors the molar production 0.4403
0.6 ofofsyngas,
syngas.itHowever,
is recommended the growth to work 0.6 with ER values between 0.3 and 0.5 and low SBR.
in SBR, in addition to increasing the composition of H2 ,
Steam to biomass ratioSteam to biomass ratio
0.3956 0.4135
increases the composition of CO2 .
0.3719 0.3868
0.4 0.4
Molar flow (kmol/h)
0.3483
Molar flow0.3600
(kmol/h)
0.4430 0.4670
0.3246 0.3333
0.4193 0.4403
0.6 0.6
0.2 0.3009 0.2 0.3065
0.3956 0.4135
0.2772 0.2798
0.3719 0.3868
0.4
0.0
0.2535
0.00.4
0.2530
0.3483 0.3600
0.2 0.4 0.6 0.2 0.4 0.6
Equivalence ratio 0.3246
Equivalence ratio 0.3333
0.2 0.3009 0.2 0.3065
0.2772 0.2798
0.2535 0.2530
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6
Figure 16. Cont.

Mass flow (kg/h) Mass flow (kg/h)

8.170 8.270
7.813 7.900
0.6 0.6

7.455 7.530
7.098 7.160
0.4 0.4
6.740 6.790
6.383 6.420
0.2 6.025
0.2 6.050
5.668 5.680
5.310 5.310
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6

Figure
Figure 16.16. Combined
Combined effects
effects of and
of ER ER and
SBRSBR onmolar
on the the molar and mass
and mass flow
flow of of syngas
syngas produced
produced with hardwood
with hardwood chips (a)chips (a) and
and almond
almond
shells (b). shells (b).
It is also observed
3.5.5. Temperature thatGasifier
of the the increase of both ER and SBR rises the mass flow of syngas.
As observed in the molar flows, after ER values of 0.4 and 0.5 (hardwood chips and almond
The analysis of the SBR influence showed that the growth in steam decreases the
shells, respectively) there is a decrease in the molar flow caused by the decline of H2 and
temperature ofSBR
the increase in gasification.
favors theThe previousofER
composition H2study showed
, but also thatthe
increases thecomposition
increase in of
airCO
initially
2.
lowers the gasification
Thus, although temperature
the ER and andthe
SBR increase that
massafter
flow0.4of(for hardwood
syngas, chips)
this flow andhave
may not 0.45 (for
almond
the bestshells) the temperature
compositions starts
of H2 and CO. to rise.in
Therefore, Figure
relation17toshows the combined
the production influence
of syngas, it is of
these two parameters in the reaction temperature for both
recommended to work with ER values between 0.3 and 0.5 and low SBR. biomasses. The decreasing tem-
perature with increasing steam was evident with any value of ER. However, it should be
3.5.5. that
noted Temperature of the Gasifier
the behavior of decreasing the temperature and then rising when the ER is
The analysis of
increased does not happen inthe SBR influence
all steam showed
input that the growth
values. It can be in steam decreases
observed that fromthe the
temperature of gasification. The previous ER study showed that the
steam to biomass ratio of 0.1, the gasification temperature does not decrease and thenincrease in air initially
lowers the
increases gasification
with temperature
the variation andintake.
of the air that after 0.4 (for
A rise hardwood
in the temperaturechips) only
and 0.45 (for with
occurs
almond shells) the temperature starts to rise. Figure 17 shows the combined influence
the surge of ER. This can be explained by the fact that the steam input ends up favoring
of these two parameters in the reaction temperature for both biomasses. The decreasing
more than the others the formation reactions of H2 water gas shift reaction (8) and steam–
temperature with increasing steam was evident with any value of ER. However, it should
methane
be notedreforming (10). And
that the behavior as steam–methane
of decreasing reforming
the temperature is endothermic
and then rising whenwith the ERan en-
thalpy five times greater than the water gas shift reaction, the tendency
is increased does not happen in all steam input values. It can be observed that from the is for the gasifica-
tion temperature
steam to biomasstoratio
reduce. However,
of 0.1, as of the
the gasification input of 0.1
temperature SBR,
does notonly the water
decrease gas shift
and then
reaction
increasesiswith
favored because of
the variation thetheCH that was
air4 intake. available
A rise was consumed.
in the temperature only Therefore,
occurs withthere
will
the be a greater
surge release
of ER. This canofbeenergy thanbyconsumption.
explained the fact that theThus,
steamfrominput0.1ends
to steam to biomass
up favoring
morethe
ratio, than the others the
temperature formation
tends to onlyreactions
rise with of the
H2 water gas of
increase shift
ER.reaction (8) and steam–
methane reforming (10). And as steam–methane reforming is endothermic with an enthalpy
five times greater
Gasifier than
temperature (°C) the water gas shift reaction, the tendency is for thetemperature
Gasifier gasification
(°C)
temperature to reduce.1188
However, as of the input of 0.1 SBR, only the water gas shift1344
reaction
0.6 is favored because 1118 the CH
4 that was available
0.6 was consumed. Therefore, there 1255 will be a
greater release of1048 energy than consumption. Thus, from 0.1 to steam to biomass ratio, the
1165
temperature tends 978.0

to only rise with the increase of ER. 1076
0.4 0.4
908.0 986.0
838.0 896.5
0.2 768.0
0.2 807.0
698.0 717.5
628.0 628.0
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6

Figure 17. Combined effects of ER and SBR on the temperature of the gasifier operated with hardwood chips (a) and
almond shells (b).
methane reforming (10). And as steam–methane reforming is endothermic with an en-
thalpy five times greater than the water gas shift reaction, the tendency is for the gasifica-
tion temperature to reduce. However, as of the input of 0.1 SBR, only the water gas shift
reaction is favored because the CH4 that was available was consumed. Therefore, there
will be a greater release of energy than consumption. Thus, from 0.1 to steam to biomass
ratio, the temperature tends to only rise with the increase of ER.

1188 1344
1118 1255
0.6 0.6

1048 1165
978.0 1076
0.4 0.4
908.0 986.0
838.0 896.5
0.2 768.0
0.2 807.0
698.0 717.5
628.0 628.0
0.0 0.0
0.2 0.4 0.6 0.2 0.4 0.6

Figure 17. 17.
Figure Combined effects
Combined effectsofofER and SBR
ER and SBRononthethe temperature
temperature ofgasifier
of the the gasifier operated
operated with hardwood
with hardwood chips
chips (a) and (a) and
almond
almond shells
shells (b). (b).
Thus, with the analysis of the influence of the variation of ER and SBR in the com-
position of syngas for CO, H2 , CO2, and CH4 , it can be inferred that a combination of ER
between 0.3 and 0.5 and SBR up to 0.2 is the range in which the best CO and H2 composi-
tions are obtained, with small amounts of CO2 and CH4 . These compositions are obtained
at temperatures between 850 and 950 ◦ C.
4. Conclusions
In this work, a downdraft gasifier was modeled and simulated for two residual
biomasses (forest and agricultural) in order to predict the composition of the syngas
produced. The reactors simulated gasification by minimizing the free energy of Gibbs.
The main operating parameters were the equivalence ratio, steam to biomass ratio, and
gasification temperature. In the simulations, a sensitivity analysis was carried out, where
the effects of these parameters on the composition of syngas, flow of syngas, and heating
values were studied.
The model is able to predict the gasifier’s performance and is qualified to analyze the
behavior of the independent parameters in the gasification results. The following are the
main results achieved with the simulation:
• The mass flow of syngas is favored by the increase of ER and SBR;
• The molar flow upsurges with higher SBR, however, it reaches a maximum value with
rising ER;
• The heating value of the syngas declines with increasing ER and SBR, but increases
with the growth of gasification temperature;
• The composition of H2 and CO2 improves with SBR increase, while CO declines
continuously;
• An SBR value up to 0.2 is an acceptable value to promote the production of H2 without
so much formation of CO2 in the syngas;
• The equivalence ratio is a key parameter in the process as it favors the production
of H2 . A low amount causes the absence of gasification and a high amount causes
formation of CO2 , decrease of CO, and the presence of N2 in the synthesis gas;
• An ER value between 0.3 and 0.5 is within the favorable range to maximize the amount
of CO and H2 in the process;
• The favorable temperature of the gasifier must be between 850 and 950 ◦ C, controlling
the feeds of air and steam to obtain these values.
Additionally, it is concluded that in the specific conditions where the gasification
temperature is specified and changed for a fixed air intake, the content of CO tends to rise
with increasing temperature, but the content of H2 reaches a maximum for an optimal
temperature value, while CO2 and CH4 tend to decrease continuously.
In summary, with a temperature between 850 and 950 ◦ C, SBR values up to 0.2 and
ER values between 0.3 and 0.5, the best operating conditions are obtained to maximize the
composition of the syngas rich in CO and H2 .
Author Contributions: Conceptualization, M.P., P.B., H.T.G. and A.V.; methodology, M.P., P.B. and
H.T.G.; validation, M.P., P.B. and H.T.G.; formal analysis, M.P., P.B., H.T.G. and A.V.; investigation,
M.P., P.B., H.T.G. and A.V.; resources, P.B., H.T.G.; writing—original draft preparation, M.P.; writing—
review and editing, P.B., H.T.G. and A.V.; supervision, P.B., H.T.G. and A.V. All authors have read
and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.
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chemengineering

Keywords: biomass gasification; downdraft gasifier; process simulation; UniSim Design

Received: 27 February 2021

ChemEngineering 2021, 5, 20. https://doi.org/10.3390/chemengineering5020020 https://www.mdpi.com/journal/chemengineering

Table 1. Main reactions involved in the gasification processes.

Gasification Step Reaction ∆H◦ (kJ/mol)

Figure 1. Downdraft gasifier.

Table 2. Approximate and ultimate analysis of the biomass stocks [28,29].

Biomass Feedstock Hardwood Chips Almond Shells

Table 3. Input parameters in the simulation study.

2.3. Simulation Basis Manager

Hardwood Chips Almond Shells

3. Results and Discussion

Table 5. Parameters considered in the base simulations.

Hardwood Chips Almond Shells

Table 6. Main simulation streams for hardwood chips.

Biomass Flue Gases To Gasif Gasif Gases Product Gases Syngas

Table 7. Main simulation streams for almond shells.

Biomass Flue Gases To Gasif Gasif Gases Product Gases Syngas

Table 8. Parameters and results of reference studies [27,29].

3.2. Effect of Equivalence Ratio

ChemEngineering 2021, 5, 20 3.2.1. Molar Composition of Syngas 11 of 24

Syngas mole composition (%)

(a) hardwood chips (b) almond shells

0.38 7.0 0.38 7.0

Syngas molar flow (kmol/h)

Syngas mass flow (kg/h)

0.32 6.2 0.32 6.2

0.30 6.0 0.30 6.0

(a) hardwood chips (b) almond shells

Heating value (MJ/kg)

(a) hardwood chips (b) almond shells

3.2.4. Gasifier Temperature

ChemEngineering 2021, 5, 20 3.2.4. Gasifier Temperature 13 of 24

Usually, the gasification temperature is analyzed as an independent variable depend-

Gasifier temperature (°C)

(a) hardwood chips (b) almond shells

3.3. Effect of Steam to Biomass Ratio

3.3.1. Molar Composition of Syngas

Syngas mole composition (%)

(a) hardwood chips (b) almond shells

0.48 8.0 0.48 8.0

Syngas molar flow (kmol/h)

Syngas mass flow (kg/h)

0.42 7.2 0.42 7.2

0.40 7.0 0.40 7.0

(a) hardwood chips (b) almond shells

3.3.3. Heating Value

(a) hardwood chips (b) almond shells

3.3.3. Heating Value

Heating value (MJ/kg)

(a) hardwood chips (b) almond shells

3.3.4. Gasifier Temperature

3.4. Effect of the Temperature of the Gasifier

Gasifier temperature (°C)

(a) hardwood chips (b) almond shells

Syngas mole composition (%)

Syngas mole composition (%)

(a) hardwood chips (b) almond shells