International Journal of Hydrogen Energy 49 (2024) 1518–1527

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International Journal of Hydrogen Energy

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Hydrogen production from supercritical water gasification of

canola residues
Kapil Khandelwal a, Sonil Nanda b, Philip Boahene a, Ajay K. Dalai a, *
a
Department of Chemical and Biological Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada
b
Department of Engineering, Faculty of Agriculture, Dalhousie University, Truro, Nova Scotia, Canada

A R T I C L E I N F O A B S T R A C T

Handling editor: Jinlong Gong Canola hull, meal and straw are abundantly available as low-value agricultural residues in Canada. These
lignocellulosic feedstocks have the potential for the generation of biofuels as alternatives to fossil fuels. Super­
Keywords: critical water gasification is an emerging hydrothermal process for the conversion of recalcitrant biomasses into
Canola residue value-added hydrogen with the application of water beyond its critical temperature and pressure. This study
Hydrochar
focuses on the comparative investigation of supercritical water gasification of canola residues for H2 production
Biofuel
through optimization of process temperature (350–500 ◦ C), reaction time (20–80 min) and feedstock concen­
Hydrogen
Lignocellulosic biomass tration (10–25 wt%) at a constant pressure of 23–25 MPa. Supercritical water gasification of canola straw
Supercritical water gasification resulted in a high H2 yield of 7.1 mmol/g to 6.2 mmol/g of H2 from canola hull and 5.5 mmol/g of H2 from
canola meal at a temperature, reaction time and feedstock concentration of 500 ◦ C, 40 min and 20 wt%,
respectively. Furthermore, H2 yield and total gas yield from canola straw were maximized to 8.1 mmol/g and
29.7 mmol/g at the optimized supercritical water gasification conditions of 500 ◦ C, 60 min and 10 wt%.
Hydrochar obtained at high gasification temperatures also revealed aromatic carbon structures and thermal
stability due to dehydrogenation, decarboxylation, deamination and aromatization. The overall results demon­
strated the potential of supercritical water gasification as an evolving hydrothermal process to convert ligno­
cellulosic biomass into high-value H2-rich gas.

1. Introduction production of 20 million metric tonnes in 2022 with a projection to

reach 26 million tonnes by 2025 [3]. Canada also has the highest
Greenhouse gas emissions from the exploitation of fossil fuels to number of established canola meal processing units in the world and is
quench the demands of the rapidly developing global economies have home to 14 crushing and refining plants to process 11 million tonnes of
led to a plethora of environmental threats such as global warming, rising canola seeds. These industries primarily produce canola oil for refineries
sea levels, health hazards and climate change [1]. This ever-increasing to produce edible cooking and vegetable oils. Canola processing also
global energy demand in addition to these environmental concerns produces significant amounts of residues such as hull, meal and straw.
has created a pressing need for sustainable alternative sources of energy. These canola residues are currently used as efficient sources of palatable
The utilization of hydrogen (H2) as an energy source has the potential to protein for livestock, poultry and fish. However, large amounts of phytic
overcome the challenges of energy security and the derivation of clean acid, sinapyl alcohol and tannins in canola meal could lead to poor di­
energy from waste resources. Despite the promising prospect of H2 as an gestibility in certain cattle making it undesirable as animal feed [4,5]. In
energy source, its global demand in 2021 was 94 million tonnes, addition, a substantial amount of canola residues remains underutilized.
equivalent to nearly only 2.5 % of global energy consumption [2]. Sustainable utilization of these low-value canola residues into
Furthermore, more than 95 % of H2 is commercially produced from high-value clean fuels and chemicals has a great potential for improving
non-renewable sources primarily via steam methane reforming of nat­ biomass utilization and value addition to support canola industries and
ural gas, which emits a significant amount of greenhouse gases. farmers.
Canada is the largest producer and exporter of canola with an annual Supercritical water gasification (SCWG) is recently gaining

* Corresponding author. Distinguished Professor and Canada Research Chair Department of Chemical and Biological Engineering University of Saskatchewan
Saskatoon, Saskatchewan, Canada.
E-mail address: [email protected] (A.K. Dalai).

https://doi.org/10.1016/j.ijhydene.2023.10.228
Received 10 August 2023; Received in revised form 17 October 2023; Accepted 23 October 2023
Available online 18 November 2023
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
K. Khandelwal et al. International Journal of Hydrogen Energy 49 (2024) 1518–1527

of 374 ◦ C and 22.1 MPa [7]. At these conditions, supercritical water

(SCW) has both liquid and gas-like properties, which imparts unique
properties and advantages to SCWG such as low mass resistance, the
high solubility of product gases, easy separation of salts and impurities
and high reaction rate [8].
A large database of literature is available for SCWG of various

Fig. 1. Gas yields from SCWG of canola residues at temperature, reaction time,
feed concentration and pressure of 500 ◦ C, 40 min, 20 wt% and 23–25 MPa,
respectively.

Table 1
Total gas yield, hydrogen selectivity and lower heating value of gaseous prod­
ucts from SCWG of canola residues.
Gasification conditions Total gas H2 selectivity LHV Fig. 2. Effects of temperature on gas yields from SCWG of canola straw at the
yield (mmol/ (%) (kJ/ reaction time, feed concentration and pressure of 40 min, 20 wt% and 23–25
g) Nm3) MPa, respectively.
500 ◦ C, 40 min, 20 wt Canola 20.6 22.1 3506
% and 23–25 MPa hull
Canola 24.8 24.9 3663
meal
Canola 25.4 27.9 3476
straw
Canola straw (40 min, 350 ◦ C 13.4 20.3 1152
20 wt% and 23–25 400 ◦ C 16.2 25.9 1609
MPa) 450 ◦ C 22.0 27.5 2866
500 ◦ C 25.4 27.9 3476
Canola straw (500 ◦ C, 20 min 18.2 23.1 2541
20 wt% and 23–25 40 min 25.7 27.5 3520
MPa) 60 min 27.3 27.1 3566
80 min 26.4 26.6 3638
Canola straw (500 ◦ C, 10 wt% 29.7 27.4 4271
60 min and 23–25 15 wt% 28.4 27.2 3964
MPa) 20 wt% 27.3 27.1 3566
25 wt% 22.0 23.7 3029

popularity for transforming lignocellulosic biomass, municipal solid

waste, non-plant residues and other complex organic materials into H2-
Fig. 3. Effects of reaction time on gas yields from SCWG of canola straw at
rich syngas [6]. SCWG utilizes water as its solvent at supercritical con­ temperature, feed concentration and pressure of 500 ◦ C, 20 wt% and 23–25
ditions i.e., temperature and pressures greater than water’s critical point MPa, respectively.

Table 2
Characterization of canola residues and hydrochar samples.
Content Canola Canola Canola Canola straw hydrochar Canola straw hydrochar Canola hull hydrochar Canola meal hydrochar
straw hull meal (350 ◦ C) (500 ◦ C) (500 ◦ C) (500 ◦ C)

Carbon (wt%) 46.3 43.8 50.6 69.4 71.1 50.9 54.3

Hydrogen (wt%) 6.8 6.0 5.5 4.7 3.3 2.8 3.1
Nitrogen (wt%) 0.9 1.3 6.4 0.7 0.9 0.5 4.0
Sulfur (wt%) 0.4 0.8 1.0 0.8 0.9 3.2 0.6
Oxygen (wt%) 45.6 48.1 36.5 24.4 23.9 42.6 38.0
HHV (MJ/kg) 18.9 18.1 20.5 24.5 24.0 17.9 19.0
Cellulose (wt%) 46.2 41.0 7.9 – – – –
Hemicellulose (wt 29.2 16.4 3.6 – – – –
%)
Lignin (wt%) 14.2 10.0 9.0 – – – –
Crude protein (wt – – 34.0 – – – –
%)

Note: Oxygen content was calculated on an ash-free basis. Hydrochar samples were generated from SCWG with 20 wt% feed concentration in 40 min under 23–25 MPa
pressure.

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Table 3
Summary of recent studies of SCWG of agricultural crop residues.
Feedstocks Process conditions Main findings Reference

Almond shells, • Temperature: • Wheat straw Safari

walnut shells 440 ◦ C demonstrated the et al. [39]
and wheat • Pressure: 25 MPa highest H2 yield of
straw • Reaction time: 5–30 6.5 mmol/g
min followed by walnut
• Feedstock shells and almond
concentration: 1 wt shells.
% • The highest H2 yield
• Optimized reaction from wheat straw
condition: 440 ◦ C, was due to its
10 min and 1 wt% highest cellulose
(feedstock content (40 %)
concentration) followed by walnut
shell (36 %) and
almond shell (31
%).
Fig. 4. Effects of feedstock concentration on gas yields from SCWG of canola • Further
straw at temperature, reaction time and pressure of 500 ◦ C, 60 min and 23–25 optimization of
MPa, respectively. reaction time
improved the H2
yield from SCWG of
feedstocks such as agricultural biomass [9], forestry residues [10], black wheat straw to 7.3
liquor [11], algae [12], food waste [13], fruit pulp [14], plastics [15], mmol/g.
Barley straw • Temperature: • High temperature, Sarker
wastewater [16] and sewage sludge [17]. These studies have demon­
pellets, canola 300–500 ◦ C reaction time and et al. [40]
strated the potential of SCWG technology for processing a wide variety hull pellets • Pressure: 22–25 biomass/water
of feedstocks into H2-rich syngas. However, despite the abundance of and oat hull MPa ratio were
canola residues and the advantages of the SCWG process, few efforts pellets • Reaction time: beneficial for total
have been made to utilize these residues for SCWG. Most of the studies 20–60 min gas yield and H2
• Biomass/water yield from SCWG of
available on the valorization of canola residues via thermochemical
ratio: 1:5–1:15 canola hull pellets.
waste-to-energy processes primarily involved torrefaction [18], pyrol­ • Reactor type: Batch • The highest H2
ysis [19] and hydrothermal liquefaction [20]. Some of the recent studies • Optimized reaction selectivity and total
have involved the pelletization of canola residues using binders and condition: 500 ◦ C, gas yields of 52 %
60 min and 1:10 and 7.3 mmol/g
additives before their thermochemical conversion to bioenergy products
(biomass/water were obtained at
[21–24]. ratio) the optimized
A comparative investigation of the physicochemical properties of reaction condition
different canola residues and their behavior during SCWG is one of the of 500 ◦ C, 60 min
main knowledge gaps in the literature. Hence, it is important to compare and 1:10 biomass/
water ratio from
the performance of different canola residues at similar process condi­
SCWG of canola
tions and reactor types and to avoid process variability. Furthermore, hull pellets.
the literature on the effects of process conditions such as temperature, • SCWG of canola
reaction time and feedstock concentration on SCWG of different canola hull pellets
residues is also scarce. Hence, in this study, a comparative evaluation of demonstrated the
highest H2 and total
H2-rich syngas production from SCWG of different canola residues i.e., gas yields.
hull, meal and straw is made while providing new insights into the Canola hull, • Temperature: • SCWG of canola This study
impacts of SCWG process conditions on the product distribution and canola meal 350–500 ◦ C straw demonstrated
properties of product gases and hydrochar. and canola • Pressure: 23–25 the highest H2 and
straw MPa total gas yields
The literature on SCWG reports various studies on the optimization
• Reaction time: among all the
of reaction conditions for enhancing syngas yields. However, only a few 20–80 min canola residues due
studies have provided an in-depth discussion on the interrelated effects • Feedstock to its highest
of reaction conditions such as temperature, pressure, time, feed con­ concentration: cellulose and
centration and catalysts loading on gas yields from SCWG of agriculture 10–25 wt% hemicellulose
• Reactor type: Batch contents.
residues, especially canola residues. This study aims to fill in this gap by • Optimum reaction • An increase in
studying the influence of process parameters on the SCWG of canola conditions: 500 ◦ C, temperature and
residue as well as presenting a comprehensive physicochemical char­ 60 min and 10 wt% reaction time
acterization of canola residue and its hydrochar derived from SCWG. (feedstock increased the
concentration) gaseous yield,
This is important to devise conclusions on the evolution of the compo­
however, an
sitional (i.e., organic and elemental), morphological and structural increase in
features of canola residue and its hydrochar during gasification in SCW. feedstock
This can also help to understand how different types of agricultural concentration
residues could behave during their degradation in SCWG at varied re­ decreased the gas
yields.
action conditions. In addition, most studies in the literature on SCWG • The highest H2 yield
have compared different biomass. However, this study is focused on and total gas yield
studying the yields and properties of gas and hydrochar from SCWG of of 8.1 mmol/g and
different residues (i.e., hull, meal and straw) of the same type of agri­ 29.7 mmol/g,
respectively were
cultural crop (canola) which minimizes variability and extends the
benefits of a circular and all-inclusive waste valorization practice. (continued on next page)

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Table 3 (continued ) graded tubing and fittings used in the reactor assembly were sourced
Feedstocks Process conditions Main findings Reference from Swagelok (Saskatoon, Saskatchewan, Canada). A detailed
description of the experimental procedure is provided elsewhere [25].
obtained at
optimum reaction
Industrial-grade nitrogen gas was used for establishing an inert envi­
conditions of ronment and an initial pressure of 6–10 MPa based on reaction
500 ◦ C, 23–25 MPa, conditions.
60 min and 10 wt% The desired amount of feedstock (i.e., canola hull, meal and straw)
feedstock
was mixed in 10 mL of deionized water to attain the required amount of
concentration.
Canola meal and • Temperature: • An increase in Nanda feedstock concentration before loading in the reactor. The tubular batch
low-density 375–525 ◦ C temperature and et al. [41] reactor was heated to the desired reaction temperature using an ATS
polyethylene • Pressure: 22–25 reaction time for 3210 furnace (Applied Test Systems, Butler, USA), which was controlled
(LDPE) MPa SCWG of canola by an ATS temperature controller. The temperature in the reactor was
• Reaction time: meal increased the
15–60 min total gas yields and
monitored by a K-type thermocouple (Omega Sensing Solutions ULC, St-
• Biomass/water H2 yield. Eustache, Quebec, Canada). Upon the completion of the gasification, the
ratio: 1:10 • Co-gasification of reaction products were collected in a gas-liquid separating cylinder (i.e.,
• Catalyst: WO3–TiO2, canola meal with condenser) followed by the collection of liquid products and gases. A
KOH, TiO2, ZrO2 LDPE demonstrated
dehydrating desiccant column (LabClear Drierite®) procured from
and WO3–ZrO2 synergistic behavior
• Reactor type: Batch on gas yields. Avantor VWR (Edmonton, Alberta, Canada) was used for the removal of
• Optimum reaction • The highest total only moisture from the gas product as it immediately exited from the
conditions: 525 ◦ C, gas yield of 17.9 gas-liquid separating cylinder for collection in a gas bag for analysis in a
1:10 (biomass/ mmol/g and H2 gas chromatography (GC) system. The Drierite® is a molecular sieve
water ratio) and 60 yield of 8.1 mmol/g
min were obtained from
desiccant selective for the removal of moisture, oil and impurities from
non-catalytic SCWG inert gases such as N2, Ar, He and H2. Molecular sieve adsorbents are
at optimal reaction synthetic zeolites that are known to have better moisture absorption
conditions of properties compared to silica gel or clay [26]. The primary function of
525 ◦ C, 1:10
this desiccant filter is to remove moisture and oil particles to safeguard
(biomass/water
ratio) and 60 min the GC column.
with canola meal
and LDPE blending 2.3. Characterization of feedstock and SCWG products
ratio of 1:1.
In catalytic SCWG,
The elemental analysis of canola residues and the hydrochar samples
•
WO3–TiO2
improved H2 yield resulting from their SCWG was performed in an Elementar Vario EL III
to 18.5 mmol/g. CHNS analyzer (Elementar Analysensysteme, Hanau, Germany).
Food waste • Temperature: • H2 yield and total Su et al. Compositional analysis of canola residues was performed in an ANKOM
420–480 ◦ C gas yields increased [42]
200 Fiber Analyzer (ANKOM Technology, Macedon, New York, USA)
• Pressure: 26–30 from 2.3 mmol/g
MPa and 5.2 mmol/g, using the modified Van Soest method [27]. The higher heating values
• Reaction time: 40 respectively at (HHV) of feedstock and hydrochar samples were calculated using Eq.
min 420 ◦ C to 4.9 (1):
• Feedstock mmol/g and 12.7 ( )
concentration: 8 wt mmol/g at 480 ◦ C. MJ
% • The increase in gas
HHV = (0.3137 × Cwt%) + (0.7009 × Hwt%)
Nm3
• Optimum reaction yields was due to
conditions: 480 ◦ C, enhancement in + (0.0318 × Owt%)− 1.3675 (1)
40 min and 8 wt% endothermic
(feedstock reforming reaction Thermogravimetric analysis (TGA) and differential thermogravi­
concentration) at high metric analysis (DTG) of canola residues and the hydrochar samples
temperatures. were done to determine their thermal stability and degradation
• The use of 6 % La- behavior. The analysis was performed in a Q500 TGA instrument (TA
promoted Ni/Al2O3
Instruments-Waters LLC, New Castle, USA) using an N2 environment
catalysts improved
H2 yield to 8 mmol/ with a heating rate of 10 ◦ C/min up to 600 ◦ C. Fourier-transform
g. infrared (FTIR) spectroscopy of canola residues and the hydrochar
samples was done to analyze the occurrence of different surface organic
functional groups. The analysis was conducted using a Bruker Vertex
2. Methods and materials 70v FTIR spectrometer (Bruker Corporation, Billerica, USA). 13C cross-
polarization/total suppression of sideband (13C CP/TOSS) analysis for
2.1. Feedstock preparation
the hydrochar samples was determined using solid-state nuclear mag­
netic resonance (NMR) spectroscopy using a Bruker AVANCE III HD
Canola straw and hull used in this study were procured from a local
spectrometer (Bruker Corporation, Milton, Ontario, Canada).
Canadian farm, whereas canola meal was sourced from Milligan Bio The gaseous products from SCWG of canola residues were analyzed
(Foam Lake, Saskatchewan, Canada). All the feedstocks were air-dried
using an Agilent 7820A gas chromatography instrument equipped with
and ground using an industrial-grade knife mill and sieved to an a thermal conductivity detector, an Ultimetal Hayesep T 80/100 mesh
average particle size of 1 mm.
column (for CO2 and C2–C4), an Ultimetal HayesepQ T 80/100 mesh
column (for H2, CO and CH4) and an Ultimetal Molsieve 13 80/100 mesh
2.2. Experimental set-up for supercritical water gasification column (for N2 and O2). All the gas products (H2, CH2, CO, CO2 and
C2–C4) were quantified using Eq. (2):
All the SCWG experiments were conducted in a stainless steel
(SS316) tubular batch reactor. The dimensions of the reactor were 1.3
cm outer diameter, 0.9 cm internal diameter and 4 cm length. SS316-

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Fig. 5. Thermogravimetric analysis and differential thermogravimetric analysis of (a) canola straw, (b) canola hull and (c) canola meal with respective hydro­
char samples.

Produced moles of gas (mmol) (Table 1). Cellulose and hemicellulose are made up of hexose and
Yieldgas (mmol/g) = (2)
Total mass of feedstock (g) pentose sugar which are easier to degrade into small reactive sugar
molecules to produce gaseous molecules during SCWG [28,29]. On the
Hydrogen selectivity was determined using Eq. (3):
other hand, canola meal contained a high amount of protein (34 wt%)
Hydrogen yield (mmol) which was also indicated by its high nitrogen content of 6.4 wt%
H2 selectivity (%) = ×100 (3)
Total gas yield (mmol) (Table 2). These proteins primarily consist of peptide bonds, which
make the hydrothermal degradation of canola meal slower, thus
The lower heating value (LHV) of gaseous products was calculated resulting in low yields of gases and favoring the formation of heavy
using Eq. (4): molecular weight components [30]. This was also confirmed by its
( )
kJ highest yield of C2–C4 gaseous (1.1 mmol/g) (Fig. 1).
LHV
Nm 3
= 4.2 × (30.3 × CO+25.8 × H2 +85.5 × CH4 +151.3 × Cn Hm ) Canola straw also resulted in the highest H2 yield (7.1 mmol/g)
(4) compared to canola hull (6.2 mmol/g), and canola meal (4.5 mmol/g)
during SCWG at 500 ◦ C in 40 min with 20 wt% (Fig. 1). This was also
3. Results and discussion confirmed with its highest H2 selectivity of 27.9 % compared to other
canola residues (Table 1). CO2 yield was also highest (11.3 mmol/g) in
3.1. SCWG of canola residues the case of canola straw. Interestingly, canola hull resulted in the highest
CH4 yield of 6.3 mmol/g compared to canola straw (6 mmol/g) and
SCWG of canola residues was conducted at the test temperature, canola meal (5.3 mmol/g). Canola hull also demonstrated the highest
reaction time, feed concentration and pressure of 500 ◦ C, 40 min, 20 wt LHV of 3663 kJ/Nm3 (Table 1). This was primarily due to its highest
% and 23–25 MPa, respectively. The trend of individual gas yields is yield of CH4 and C2–C4 gases which has more contribution in LHV with a
presented in Fig. 1 while the total gas yields, H2 selectivity and LHV of coefficient of 85.5 and 151.3 in Eq. (4). On the other hand, canola straw
product gases are provided in Table 1. As evident from Fig. 1, H2, CO, demonstrated the lowest LHV of 3476 kJ/Nm3 despite having the
CH4 and CO2 are primary gaseous products with trace amounts of C2–C4 highest gas yields. This was due to the high composition of H2 in product
gases from SCWG of canola residues. Among the residues, canola straw gases which have the lowest contribution to LHV. Among all the canola
demonstrated the highest total gas yield of 25.4 mmol/g followed by residues, canola straw demonstrated the highest H2 yield, H2 selectivity
canola hull (24.8 mmol/g) and canola meal (20.6 mmol/g) (Table 1). and total gas yields. Hence, canola straw was used for the optimization
The high gas yields from SCWG of canola straw were due to its higher experiments to investigate the effects of reaction parameters on SCWG.
cellulose and hemicellulose content compared to canola hull and meal

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5.1 mmol/g at 300 ◦ C to 10.1 mmol/g at 500 ◦ C at the reaction time and
the biomass-to-water ratio of 45 min and 1:5, respectively were
reported.
From Fig. 2, it is evident that the yields of CO2, CH4 and C2–C4 also
increased from 8.2 mmol/g, 1.5 mmol/g and 0.4 mmol/g at 350 ◦ C
respectively to 11.3 mmol/g, 6 mmol/g and 0.8 mmol/g at 500 ◦ C. On
the contrary, CO witnessed a drop in its yield from 0.6 mmol/g at 350 ◦ C
to 0.2 mmol/g at 500 ◦ C. Water-gas shift reaction consumes the liberated
CO from the reforming reaction to generate H2 and CO2, which explains
its decrease with the temperature increase. However, CO and CO2 can
also undergo methanation and hydrogenation reactions at high tem­
peratures to increase the production of CH4 [34]. LHV also witnessed a
rise from 1152 kJ/Nm3 at 350 ◦ C to 3476 kJ/Nm3 at 500 ◦ C with an
increase in temperature (Table 1). Due to the positive influence of re­
action temperature on H2 yield and selectivity as well as total gas yields,
500 ◦ C was selected as the optimum reaction temperature for further
optimization studies.

3.3. Effects of reaction time

The effects of reaction time on the gas yield for SCWG of canola straw
at the optimized temperature of 500 ◦ C and constant feed concentration
of 20 wt% was investigated (Fig. 3). Reaction time had a positive in­
fluence on the gas yield but up to a certain period. For instance, with an
increase in reaction time from 20 min to 60 min, total gas yields
increased from 18.2 mmol/g to 27.3 mmol/g (Table 1). However, a
further increase in the reaction time from 60 min to 80 min decreased
the total gas yield from 27.3 mmol/g to 26.4 mmol/g. A similar trend
was observed for H2 and CO2 yields which first increased from 4.2
mmol/g and 8.5 mmol/g, respectively to 7.4 mmol/g and 12.6 mmol/g
with an increase in reaction time from 20 min to 60 min. A drop in H2
and CO2 yields from 7.4 mmol/g and 12.6 mmol/g to 7 mmol/g and
11.8 mmol/g was observed with a further increase of reaction time from
60 min to 80 min (Fig. 3). On the contrary, CH4 yield and LHV witnessed
a continuous increase from 4.9 mmol/g and 2541 kJ/Nm3, respectively
to 6.5 mmol/g and 3678 kJ/Nm3 with an increase in reaction time from
20 min to 80 min.
Su et al. [35] reported an increase in H2 yield from 5.4 mmol/g at 30
min to 7 mmol/g at 60 min at the reaction temperature, feed concen­
tration and pressure of 480 ◦ C, 5 wt% and 28 MPa, respectively. They
also observed a similar rise in CH4, CO2, total gas yield and LHV of
product gas with an increase in reaction time from 30 min to 60 min.
Furthermore, Nanda et al. [9] observed a decrease in H2 yield (2.1
Fig. 6. FTIR spectroscopy of (a) canola residues biomass and (b) hydro­ mmol/g) at a longer reaction time of 70 min from 3 mmol/g at 60 min.
char samples. Interestingly, CO and C2–C4 showed an erratic trend with reaction time.
CO and C2–C4 yield first increased from 0.1 mmol/g and 0.5 mmol,
3.2. Effects of temperature respectively to 0.5 mmol/g and 0.8 mmol/g with the rise in reaction
time from 20 min to 40 min followed by a decrease to 0.3 mmol/g and
The effects of reaction temperature from 350 ◦ C to 500 ◦ C on SCWG 0.6 mmol/g in 60 min (Fig. 3). A further increase in the reaction time to
of canola straw was studied at a fixed reaction time and feed concen­ 80 min resulted in an increase in C2–C4 yield to 0.8 mmol/g, whereas CO
tration of 40 min and 20 wt%, respectively under 23–25 MPa pressure yield remained nearly the same at 0.3 mmol/g.
(Fig. 2). A rise in temperature from 350 ◦ C to 500 ◦ C significantly The increase in total gas yield was due to the formation of simple and
increased the total gas yields from 13.4 mmol/g to 25.4 mmol/g smaller molecular weight intermediate compounds, which are easily
(Table 1). The increase in gas yield with a temperature rise was due to gasified thus resulting in high gas yields [7]. High H2 gas yield with an
the endothermic nature of reforming and hydrolysis reaction, which increase in reaction time can be attributed to the promotion of reforming
enhanced the biomass degradation during SCWG to produce H2 and CO and water-gas shift reactions at longer reaction times [36]. The initial
at high temperatures [31]. Similarly, H2 yield increased 2.5 folds from increase in CO and H2 yields with a rise in reaction time from 20 min to
2.7 mmol/g to 7.1 mmol/g and H2 selectivity also increased from 20.3 % 40 min indicated the enhancement of the reforming reaction which
to 27.9 % with an increase in the temperature from 350 ◦ C to 500 ◦ C. subsequently increased the production of CH4, H2, CO2 and C2–C4 gases.
This indicates the favorability of H2 production at high temperatures. However, a decline in CO yield with a further increase in the reaction
High H2 yield at high temperatures was primarily due to the dominance time from 40 min to 60 min suggested the activity of methanation and
of the free radical reactions, which favor water-gas shift reaction by water-gas shift reaction, which consumed CO to selectively produce
consuming CO to produce H2 and CO2 [32]. Okolie et al. [33] also CH4, H2 and CO2. Moreover, a further increase in the reaction time to 80
observed a positive effect of reaction temperature on total gas yield and min resulted in the dominance of methanation and repolymerization
H2 yield for SCWG of soybean straw. An increase in total gas yield from reactions, which continued enhancing the yields of CH4 and C2–C4 while
decreasing H2 and CO2 yields. This was further reinforced by a

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13
Fig. 7. C CP/TOSS solid-state NMR spectroscopy of hydrochar samples from SCWG of canola residues.

continuous increase in LHV of gaseous products and a plateau of CO 500 ◦ C, 60 min and 10 wt% feedstock concentration.
yield. Overall, the decrease in H2 and CO2 yields was more significant
compared to the increase in CH4 and C2–C4 yields, thus resulting in a 3.5. Interrelated mechanisms during SCWG of biomass
decline in total gas yields as the reaction time prolonged from 60 min to
80 min. Hence, in this study, the optimal reaction time for SCWG was 60 Table 3 summarizes the findings of this study with some recent re­
min. ports on SCWG of agricultural crop residues. As discussed earlier,
regardless of the biomass type, their hydrothermal degradation during
3.4. Effects of feedstock concentration SCW undergoes the following reactions [43,44].

Reforming reaction: Biomass + H2O → CO + H2 Eq. (5)

The effects of feedstock concentration on SCWG of canola straw at
the optimized temperature and reaction time of 500 ◦ C and 60 min are Water-gas shift reaction: CO + H2O ⇄ CO2 + H2 Eq. (6)
presented in Fig. 4. Total gas yield increased from 22 mmol/g at 25 wt%
to 29.7 mmol/g at 10 wt% feedstock concentration from SCWG of canola Methanation reaction: CO + 3H2 ⇄ CH4 + H2O Eq. (7)
straw (Table 1). A similar rise in the yields of H2, CH4, CO2 and C2–C4 Hydrogenation reaction: CO + 2H2 → CH4 + O2 Eq. (8)
was observed from 5.2, 5.9, 9.7 and 0.4 mmol/g at 25 wt% to 8.1, 7.4, 13
and 1.2 mmol/g, respectively at 10 wt% feedstock concentration. The Lignocellulosic biomass first degrades via reforming reaction in the
LHV and H2 selectivity also increased from 3029 kJ/Nm3 and 23.7 % at presence of water to produce H2 with CO (Eq. (5)). Since this reaction is
25 wt% respectively to 4271 kJ/Nm3 and 27.4 % at 10 wt% feedstock endothermic and water behaves as the reactant, an increase in reaction
concentration. However, CO yield continuously increased with the rise temperature enhances reforming reactions to improve H2 production.
in feedstock concentration due to the lower activity of water-gas shift, Similarly, according to Le Chatelier’s principle, an increase in water
methanation and hydrogenation reactions (Fig. 4). content or decrease in feedstock concentration shifts the equilibrium to
An increase in total gas yield was due to the enhancement of the product side producing more H2 gas. Within short reaction times,
reforming and hydrolysis reactions of biomass at low feedstock con­ biomass does not get sufficient time to gasify and produce stable in­
centration, which improves the conversion of biomass into gaseous termediates, thus resulting in lower gas yields [45]. This is reflected by
products [37]. Water acts both as a reactant and reaction medium in the rise in gas yield with an increase in reaction temperature and a
hydrothermal gasification reactions. According to Le Chatelier’s prin­ decrease in feedstock concentration. It also explains the low gas yields at
ciple, at low feedstock concertation, the water content of total feed short reaction times.
relatively increases, which increases the rate of hydrolysis and reform­ The CO gas produced from the reforming reaction can react with
ing reactions [38]. This is also evident in the increase in the yield of H2 excess water via the water-gas shift reaction to produce H2 and CO2 (Eq.
and CO2. Similarly, the methanation reaction also enhances at low (6)). Water-gas shift reaction is endothermic and utilizes water as a
feedstock concentration resulting in high CH4 yield at 10 wt% feedstock reactant. Therefore, an increase in reaction temperature and a decrease
concentration (Fig. 4). Due to the high amount of H2 and total gases with in feedstock concentration increases H2 yield along with an increase in
complete utilization of CO, 10 wt% was the optimum feedstock con­ CO2 yield [46]. To enable the water-gas shift reaction, sufficient CO
centration. Therefore, the optimum reaction condition for SCWG of concentration is required. Thus, CO concentration first increases with an
canola straw for maximizing H2 and total gas yield was determined as increase in reaction time due to enhancement in reforming reaction and

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K. Khandelwal et al. International Journal of Hydrogen Energy 49 (2024) 1518–1527

further decreases due to its consumption as a reactant in the water-gas The FTIR analysis of canola residues is presented in Fig. 6a. FTIR
shift reaction. CO can also undergo methanation or hydrogenation re­ peak at 3296 cm− 1 represents the O–H groups of alcohols and phenolic
actions to produce CH4 (Eq. (7) and Eq. (8)). Although the methanation compounds present in crystalline cellulose. Significant peaks at 2844
reaction is not directly influenced by feedstock concentration, it requires cm− 1 and 2923 cm− 1 were assigned to C–H bonds of methoxy groups
CO, the production of which is dependent on feedstock concentration and aliphatic groups arising from lignin [49]. The peaks at 2356 cm− 1
and high temperatures to promote biomass reforming [47]. An increase and 2923 cm− 1 represented nitro and amine groups, respectively due to
in reaction time also favors the formation of gaseous molecules which the high protein content in canola meal [50]. The peak at 1745 cm− 1
results in enhancement in CH4 yield. showed the presence of acetyl groups in hemicellulose. The peaks at
At longer reaction times, polymerization of gaseous molecules can 1409 cm− 1 and 1645 cm− 1 signified the presence of methoxyl groups
occur resulting in the formation of heavy molecular weight compounds and aromatic rings from lignin, respectively. A broader spectrum be­
such as tar and polymeric char [48]. This not only results in a decline in tween 300 and 700 cm− 1 represented the presence of aromatic C–H
gas yield but also causes operational problems of plugging, corrosion groups. The major peak around 1008 cm− 1 was due to the presence of
and pressure drop. The yield of CO depends on a series of consecutive C–– O alcohols, esters and ethers.
and competitive reactions such as reforming, water-gas shift, hydroge­ The FTIR spectra of hydrochar samples are presented in Fig. 6b. It
nation and methanation, thus resulting in its changeable trend with should be noted that the peaks at 1745 cm− 1 and 3296 cm− 1 originally
reaction time. A small rise in CH4 yield even at a longer reaction time present in canola residues were not visible in the FTIR spectra of
indicates the dominance of methanation reactions [33]. hydrochar samples representing the near-complete conversion of
hemicellulose and cellulose during SCWG. The peaks at 2956 cm− 1
3.6. Characterization of feedstock and hydrochar samples present in canola residues also diminished in hydrochar with the in­
crease in SCWG temperature from 350 ◦ C to 500 ◦ C. This signified the
The physicochemical composition of canola residues is presented in degradation of lignin and proteins at higher temperatures. A sharp peak
Table 2. It can be identified that the canola straw had the highest cel­ at 1050 cm− 1 in the case of canola meal hydrochar and 1135 cm− 1 in
lulose content of 46.2 wt% followed by canola hull (41 wt%). Although canola hull hydrochar indicated the formation of C–N bonds of aromatic
canola meal had the lowest amount of cellulose (7.9 wt%) and hemi­ amines from the conversion of fatty acids and proteins. The peak at
cellulose (3.6 wt%), it was relatively rich in protein content (34 wt%). 1573 cm− 1 in canola straw and canola hull hydrochar represented C–H
The high protein content of canola meal was reflected in its highest aromatic rings. The peak at 2356 cm− 1 canola meal hydrochar indicated
nitrogen content of 6.4 wt%. N–O bonds of nitro groups. The peaks observed in the range of
The elemental hydrogen content of hydrochar samples decreased 600–1040 cm− 1 were due to the presence of cyclic aromatic groups. For
compared to that of raw canola residues indicating that most of the canola straw hydrochar, the extent of these peaks increased with an
hydrogen content of the biomass was converted into H2 gas. The high increase in reaction temperature representing the formation of aromatic
nitrogen content of canola meal was significantly reduced from 6.4 wt% compounds at high SCWG temperatures.
to 4 wt% in its hydrochar generated at 500 ◦ C. Canola straw hydrochar The hydrochar samples from canola residues were also analyzed by
13
demonstrated the highest carbon content, which increased with the rise C CP/TOSS NMR spectroscopy (Fig. 7). Chemical shifts from the
in SCWG temperature (Table 2). On the other hand, the elemental spectra were divided into three major regions based on the ppm ranges i.
hydrogen and oxygen contents of canola straw hydrochar decreased at e., 5–90 ppm (aliphatic carbon), 95–160 ppm (aromatic vinylic groups)
higher temperatures indicating dehydration, decarboxylation, dehy­ and 165–210 ppm (carbonyl groups). The spectra for canola straw and
drogenation, carbonization and aromatization of biomass. canola hull hydrochar generated at 500 ◦ C had some resemblance. For
The TGA studies showed that canola meal was a relatively more example, the intensity of aromatic-vinylic groups was higher followed
recalcitrant feedstock followed by canola hull and canola straw due to its by aliphatic carbon and carbonyl. However, the intensity of aromatic-
lowest mass loss of 72 % compared to canola straw (81 %) and canola vinylic compounds was lower in canola meal hydrochar than canola
hull (83 %) (Fig. 5a). This is further substantiated by its lowest total gas hull hydrochar and canola straw hydrochar. The intensity of aliphatic
yield compared to canola hull and canola straw. For all the feedstocks, carbon was higher in canola meal hydrochar. This indicated that the
most of the mass loss was noticed between 200 ◦ C and 400 ◦ C since the SCWG process efficiently converted most of the aliphatics present in
typical degradation of hydroxyl groups, hemicellulose and cellulose canola hull and straw compared to canola meal, which had some re­
occurs at around 200 ◦ C, 350 ◦ C and 400 ◦ C, respectively [18]. Similarly, sidual aliphatic carbon in its hydrochar.
DTG analysis also showed that for all the canola residues, three major For canola straw hydrochar, an increase in SCWG temperature from
peaks were identified in the range of 50–150 ◦ C, 200–450 ◦ C and 480 ◦ C. 350 ◦ C to 500 ◦ C, the peak area of aromatic vinyl groups increased
The first peak at around 50–150 ◦ C signified the removal of moisture and significantly. The relative peak area of aliphatic carbon decreased in
volatile matter of canola residues. The second peak at 200–450 ◦ C was hydrochar samples at 500 ◦ C. This indicates the increased conversion of
due to the degradation of cellulose and hemicellulose, whereas the third aliphatic carbon to aromatic carbon at high SCWG temperatures.
peak at around 480 ◦ C represents the degradation of lignin. Interestingly, the peak for carbonyl groups in hydrochar generated at
The TGA analysis also revealed that for hydrochar samples obtained 350 ◦ C disappeared in the hydrochar produced at 500 ◦ C. At higher
at 500 ◦ C, most of the mass loss occurred beyond 450 ◦ C (Fig. 5b and c). SCWG temperatures, these compounds completely converted leaving no
Canola meal hydrochar was the most stable with a mass loss of 22 % residual carbonyl groups in hydrochar.
followed by canola straw hydrochar (25 %) and canola hull hydrochar
(26 %). For canola straw hydrochar, an increase in reaction temperature 4. Conclusion
decreased the mass loss of hydrochar from 48 % at 350 ◦ C to 25 % at
500 ◦ C. This was due to the carbonization and aromatization of char SCWG experiments of different canola residues such as hull, meal
resulting in the formation of more stable C–C and C–H bonds [10]. and straw were performed at a constant temperature, reaction time and
Similarly, DTG analysis of hydrochar also showed that major distinct feedstock concentration of 500 ◦ C, 40 min and 20 wt%, respectively. The
peaks were identified in the region of 480–530 ◦ C in hydrochar samples high cellulose and hemicellulose content of canola straw resulted in a
obtained at 500 ◦ C. For canola straw hydrochar, an increase in SCWG high total gas yield of 25.4 mmol/g and a high H2 yield of 7.1 mmol/g.
temperature from 350 ◦ C shifted this peak from 420-490 ◦ C to An increase in temperature from 350 ◦ C to 500 ◦ C favored water-gas
480–530 ◦ C at the SCWG temperature of 500 ◦ C. This also suggests the shift, hydrolysis and reforming reaction to enhance SCWG of canola
formation of more stable aromatic carbon groups at high reaction straw to increase H2 production. H2 yield increased with the increase in
temperatures. the reaction time from 20 min to 60 min after which it declined within

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K. Khandelwal et al. International Journal of Hydrogen Energy 49 (2024) 1518–1527

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[24] Azargohar R, Nanda S, Kang K, Bond T, Karunakaran C, Dalai AK. Kozinski JA
The authors declare that they have no known competing financial
Effects of bio-additives on the physicochemical properties and mechanical
interests or personal relationships that could have appeared to influence behavior of canola hull fuel pellets. Renew Energy 2019;132:296–307.
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