Chemical Engineering Journal 457 (2023) 141004

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Review

A critical review on co-hydrothermal carbonization of biomass and

fossil-based feedstocks for cleaner solid fuel production: Synergistic effects
and environmental benefits
Sandile Fakudze, Jianqiang Chen *
Laboratory of Advanced Environmental & Energy Materials, College of Biology and the Environment, Nanjing Forestry University, 159 Longpan Road, Nanjing 210037,
PR China

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

Keywords: The co-firing of biomass and fossil-based wastes for energy production remained a promising approach for the
Biomass effective utilization of agricultural and industrial waste. However, both untreated biomass and fossil-based
Coal feedstocks or wastes are often accompanied by undesirable fuel properties, leading to serious operational
Co-hydrothermal carbonization (co-HTC)
challenges and environmental hazards. In recent years, co-hydrothermal carbonization (co-HTC) emerged as a
Environmental benefits
potential thermochemical technique for the valorization of different solid residues into eco-friendly hydrochar
Polyvinyl-chloride
Synergistic effects fuel. In this paper, the synergistic effects, environmental and economic benefits of co-treating lignocellulosic
biomass and fossil-based feedstocks such as low grade coal and polyvinyl-chloride (PVC) were critically assessed.
Based on previous studies, the co-HTC of biomass with coal or PVC resulted in significantly improved hydrochar
yield and fuel properties. The influence of reaction temperature and time on various performance indicators such
as hydrochar yield, energy yield, fuel ratio, carbon retention, dechlorination/desulfurization rate and ash index
was also discussed. The reaction temperature of 260 ◦ C and residence time of 3–4 h emerged as optimal con­
ditions for obtaining the best hydrochar yield and carbon retention rate. Meanwhile, the most robust synergistic
effects were realized under the blending ratio of 5:5 (wt%) for both biomass-coal and biomass-PVC blends. The
co-treatment of biomass and fossil-based feedstocks also resulted in reduced ash contents and high dechlorina­
tion/desulfurization rates. Previous studies attributed the enhanced carbonization and sulfur/chlorine removal
to the biomass-originated organic acids and hydroxyl groups generated during the process. Several critical
suggestions were recommended for future studies related to the co-HTC of biomass and fossil-based feedstocks.

1. Introduction
As the combustion of fossil-based solid fuels for energy production
remained one of the largest contributors of global CO2 emissions, the co-
firing of coal and plastic residues with carbon–neutral biomass attracted
wide attention from researchers as a potential strategy for CO2 reduction
in power generation plants [1,2]. Meanwhile, coal is regarded as the
largest source of electricity and the second-largest energy source [3].
However, the gradual depletion of coal reserves due to the ever-
increasing electricity demand could pose a threat to the world’s eco­
nomic development. As a result of population growth, urbanization and
economic development, global waste generation continued to increase
over recent years. In 2019, the estimated global waste was approxi­
mately 13.7 billion tons, including agricultural waste (2.0 billion tons),
forest residues (0.92 billion tons), municipal solid waste (1.7 billion
tons) and industrial waste (9.1 billion tons) [4]. Both agricultural and
forest wastes are mainly composed of lignocellulosic biomass such as
straw, bagasse, corncob, wood chips, sawdust, and others. Lignocellu­
losic biomass is has an abundance of natural polymers (cellulose,
hemicellulose and lignin), all of which can be facilely transformed into
eco-friendly biofuels [5]. Since biomass is considered a carbon–neutral
energy source, the utilization of biomass derived fuels has been widely
promoted as an alternative to fossil fuels. Subsequently, the co-
combustion of biomass and fossil-based (such as coal and PVC) has
been extensively explored, and it is reportedly beneficial in reducing
fossil-derived toxic pollutants (heavy metals, nitrogen oxides and sulfur
dioxide) and greenhouse gas (GHG) emissions [6,7]. However, due to
the low energy density and high moisture contents of biomass, boiler

* Corresponding author.
E-mail address: chenjq@njfu.edu.cn (J. Chen).

https://doi.org/10.1016/j.cej.2022.141004
Received 27 September 2022; Received in revised form 11 December 2022; Accepted 15 December 2022
Available online 23 December 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
S. Fakudze and J. Chen
performance can be significantly sacrificed. Hence, both biomass and
fossil-based feedstocks require pre-treatment to improve their fuel
properties and environmental-friendliness.
Over the years, several pre-treatment methods have been explored
by researchers worldwide towards the production of clean biofuels,
including torrefaction, pyrolysis, gasification and hydrothermal
carbonization (HTC) [8,9]. Compared to other thermochemical
methods, HTC is favoured due to the dispensable prerequisite of inten­
sive drying prior to the process [10]. The process is carried out by
heating the feedstock in an autoclave reactor at mild temperature of
180–350 ◦ C under autogenous pressure and subcritical water or catalytic
solvent [11,12]. Hydrothermal processing has been widely investigated
for the conversion of biomass feedstocks such as seaweed, microalgae,
crop straw, wood scraps and animal manure [13–16]. During HTC,
biomass-contained natural polymers (mainly cellulose and hemicellu­
lose) are converted into solid (hydrochar), liquid and some gaseous
products through a variety of reaction mechanisms including hydrolysis,
dehydration, and decarboxylation [12,17]. Güleç et al. (2021) used
thermogravimetric analysis to study effect of process conditions on the
hydrochar properties during the hydrothermal conversion of various
feedstocks including coffee residues, rice waste, whitewood, and others
[8], and reported that hemicellulose and cellulose structures were
degraded and solubilised at about 160 ◦ C and 220 ◦ C, respectively.
According to Wang et al. (2020), the HTC process can significantly
reduce the mass yield, H/C and O/C atomic ratios, meanwhile leading to
an increase in higher heating value, with an increase in reaction tem­
perature and time [12]. Therefore, hydrochar not only has fuel prop­
erties close to lignite, but is also characterized by high hydrophobicity,
which makes it an ideal solid fuel as it requires minimal drying before
combustion. According to Wang et al. (2019), hydrochar obtained via
the HTC of wood waste demonstrated enhanced hydrophobicity,
grindability and lower inorganic contents compared to its pyrolysis or
torrefaction counterpart [18]. Unlike raw biomass, hydrochar is an
energy-rich and high-carbon solid fuel with minimal oxygen, nitrogen,
sulfur, and ash contents [19,20], hence reducing combustion challenges
such as fouling, slagging, and corrosion. In terms of combustion,
hydrochar is usually accompanied by faster ignition, higher flamma­
bility, and improved combustibility compared to coal and pyrolysis-
derived hydrochar [21,22].
Another major highlight of the HTC process is that it allows for the
simultaneous treatment of multiple feedstocks through the single-pot
approach commonly known as co-hydrothermal carbonization (co-
HTC). In recent years, co-HTC emerged as a promising co-treatment
process for upgrading different feedstock combinations, including
biomass-biomass, biomass-coal and biomass-PVC fuel blends [23–25].
For instance, Lang et al. (2019) investigated the co-hydrothermal
carbonization of swine manure and corn stalk to produce hydrochar
fuel with enhanced fuel properties and combustion performance [26].
Saba et al. (2017) treated miscanthus and coal via co-HTC, and produced
hydrochars with high energy contents, and reduced sulfur and ash
contents [27]. Previously, the valorization of pomelo peel and PVC was
performed via co-hydrothermal carbonization at 220 ◦ C using citric acid
as a solvent. Notably, most studies reported the presence of synergistic
effects during co-HTC, leading to enhanced hydrochar yields, carbon
contents and higher heating values (HHVs). Meanwhile, the co-HTC of
biomass and fossil-based feedstocks led to enhanced desulfurization/
dechlorination rates.
Although there is a few review publications focused on the hydro­
thermal carbonization of different feedstocks for solid fuel production,
the co-HTC of biomass-fossil feedstocks has not been critically reviewed.
Thus, to the best of the authors’ knowledge, this is the first publication to
assess the co-valorization of biomass and fossil-based feedstocks (spe­
cifically, coal and PVC) to analyse the effect of reaction conditions on the
properties of the product hydrochars. Synergistic effects of the co-HTC
process were rigorously analyzed based on various performance in­
dicators, including hydrochar yield, carbon contents, and fixed carbon.
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Chemical Engineering Journal 457 (2023) 141004
In addition, the desulfurization/dechlorination efficiencies of biomass-
fossil based hydrochars were compared to understand the potential of
co-hydrothermal processing in reducing the environmental toxicity of
fuel blends.
2. Challenges of co-firing untreated biomass and fossil-based
feedstocks
Co-firing is the simultaneous combustion of different fuels in the
same furnace, providing a low-cost and sustainable approach to reduce
fossil fuel use and related emissions without major alterations to the
existing power plants. The co-firing of biomass and fossil based feed­
stocks offers enormous potential for the reduction of CO2 emissions from
the power industry. From the early 2000 s, biomass/coal co-firing has
been extensively instituted in existing power generation plants, mainly
in European countries, and expanding across Australia, Asia, and North
America. Significant research has also been reported on the co-firing of
coal and various biomass feedstocks such as wheat straw, cornstalk,
wood chips, sawdust, miscanthus, and many others. Li et al. (2018)
studied the combustion behaviour of miscanthus-coal blends and re­
ported that the ignition and burnout temperatures of the blended fuels
could be significantly decreased, while their combustibility index and
fuel conversion rates could be improved [28]. However, there are many
problems and challenges related to the co-firing of coal-biomass blends
for power generation. For instance, Xue et al. (2020) investigated the
formation of pollutant gases during the co-firing of coal and wheat straw
in a fluidized bed furnace and their findings showed that the co-
combustion approach was effective in reducing pollutant gases such as
NOx, SO2 and CO [2]. In addition, the co-firing of wheat straw and coal
also resulted in reduced toxic elements (Zn, Pb, Cd) in the flue gas,
however an increase of these elements was observed in the post-
combustion ash. Typically, lignocellulosic biomass such as crop straw
and stalk are characterized by lower contents of N, S and heavy metals,
hence the reduced emission during biomass-coal co-firing. Therefore, it
should be noted that the quality of biomass-fossil based fuel blends is
highly dependent on the feedstock type (see Fig. 1 and Table 1).
Another fossil-based waste that has gained increasing attention is
coal slime, which is a by-product of the coal treatment process. Its
disposal has raised serious environmental concerns due the high con­
centration of toxic metal elements. However, owing to its low energy
content, high sulfur/nitrogen, and high ash contents, the combustion of
unblended coal slime is unsuitable as it generates high pollutant emis­
sions and lower boiler performance [30]. In a previous study, Liao et al.
(2021) investigated the co-combustion of coal slime with wheat straw
and camphor wood, and found that the addition of biomass improved
the combustion reactivity of the blends, and meanwhile it significantly
decreased the ignition and burnout temperatures, and improved the
combustion stability of the fuel blends [30]. Kazagic et al. (2018)
studied the ash-related issues and gas emissions during the co-firing of
Miscanthus and wood sawdust with low-rank coals, and reported that
increasing the proportions of woody biomass in the blends led to
elevated SO2 emissions, while larger proportions of Miscanthus yielded
lower SO2 emissions [31]. Hence, it was concluded that the biomass
feedstock type also played a major role in the combustion performance
and gas emissions. For instance, the emission of nitrogen oxides typically
decreased with an increase in biomass proportion.
In recent years, the co-firing of biomass and plastic or synthetic
wastes such as polyvinyl chloride, PP, HDPE, and rubber, has also
emerged as an effective approach for waste valorization [32–34]. In
today’s world, plastic materials have become an indispensable com­
modity, hence the global demand for plastic products is steadily
growing. Since plastics originate from petroleum derivatives and are
primarily constituted of hydrocarbons, they are usually characterized by
considerably high calorific values [35]. However, due to the addition of
additive chemicals such as antioxidants, colorants and stabilizers like
chloride substances in PVC, their direct combustion or incineration is
S. Fakudze and J. Chen
Fig. 1. Fuel quality and challenges of different types of solid feedstocks [29].
usually accompanied by toxic gas emissions and poor boiler perfor­
mance [36,37]. Chen et al. (2021) stated that the high moisture content
and low energy density of untreated biomass deteriorates its combustion
properties and suppresses the overall efficiency [38]. In addition, the co-
combustion of untreated biomass-fossil blends has also been widely
linked to operational barriers such as fouling, agglomeration, slagging,
and boiler surface corrosion, which is due to the negative impact of al­
kali metals and halogens from the post-combustion ash of biomass [39].
In consideration of the above-mentioned challenges of untreated
biomass and fossil-based feedstocks, there is an urgent need for the
treatment of biomass-fossil based fuel blends prior to co-firing. Pres­
ently, the pre-treatment of biomass is generally performed separately (as
seen in Fig. 2). For instance, Ma et al. (2021) used HTC for the con­
version pomelo peel into eco-friendly solid fuel under temperatures of
180 to 240 ◦C, which was then co-fired with coal at different blending
ratios [21]. The co-combustion of coal and biochars prepared via tor­
refaction and slow pyrolysis was also studied, and the findings revealed
that the co-firing of thermally pre-treated biomass and coal significantly
enhanced the overall combustion performance [53]. According to the
results of previous works, thermochemical pre-treatment methods such
as pyrolysis and HTC, are useful in upgrading the fuel quality of biomass,
including the energy yield, carbon contents and HHV [20,54]. In addi­
tion, the pre-treatment of biomass via HTC also resulted in reduced ash
contents, S and N contents, thereby minimizing the accumulation of
toxic post-combustion residues and gas emissions. Meanwhile, SOx, NO
and dioxin emissions remained persistent challenges in low-grade coals
and plastic waste, hence, there is also an urgent need for their pre-
treatment to significantly limit their contribution to environmental
pollution. Therefore, the co-treatment of biomass-fossil based fuel
blends prior to co-firing could serve as a low-cost and sustainable
approach for the enhancement of fuel properties of biomass and
upgrading of fossil-based feedstocks. As illustrated in Fig. 2, two
different feedstocks can be pre-mixed and treated simultaneously
through a single-pot approach to reduce operational costs. Several
studies have been conducted on the co-treatment of biomass-fossil
feedstocks [24,55,56]. Thus far, the commonly applied co-treatment
techniques are based on hydrothermal carbonization and slow pyroly­
sis. Specifically, this review focuses on the co-treatment of biomass-coal
and biomass-PVC blends via hydrothermal carbonization, which is one
of the most robust techniques for the conversion of waste materials into
eco-friendly solid fuels.
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Chemical Engineering Journal 457 (2023) 141004
3. Fundamentals of hydrothermal carbonization
Hydrothermal carbonization (HTC) refers to the heating of biomass
feedstocks or organic wastes at temperatures of 180 to 350 ◦ C under
autogenous pressure. It is by far the most promising thermochemical
technique for converting wet organic feedstocks into carbon-rich prod­
ucts (hydrochar). According to Zhang et al. (2019), the HTC process
simulates the natural formation of fossil resources like coal through the
transformation of organic materials under constant heat and pressure
over long periods of time [57]. Since the HTC process is performed over
short durations of time (0.5–6 h), it is often considered as an alternative
technique for acceleration the coal formation pathway. HTC is generally
performed in an autoclave reactor (see Fig. 3), however, there are two
standard approaches that are commonly used for the HTC process. The
first uses a standalone HTC reactor with built it pressure-monitoring and
heat control, which involves placing the reactor in a microwave oven to
apply heat. The latter usually lacks pressure-monitoring, however, it still
remained the most popular in academic research, due to its inexpen­
siveness and ease of use. Reaction parameters such as temperature, time,
and pressure are critical factors that influence the process of hydro­
thermal carbonization. However, the final products of the HTC process
are also dependent on the feedstock type. Presently, there is a limited
number of studies that investigated the HTC of biodegradable waste at
pilot scale. Zaccariello et al. (2022) developed a 100 L HTC reactor
designed to operate at 300 ◦ C and 86 bar, and used it for the pre-
treatment of bio-wastes and sewage sludge [58]. According to the au­
thors, one of the major challenges of the plant was its thermal efficiency
which was very low, suggesting that the design should be improved.
During hydrothermal carbonization, organic residues are converted
into a coal-like solid material (hydrochar) which has higher carbon
contents, increased calorific value and reduced mineral contents.
Feedstocks with high moisture contents are particularly suitable for
hydrothermal carbonization, such as agricultural residues, sewage
sludge, food wastes, and industrial wastes. In the HTC of biomass or
organic waste, hemicellulose, cellulose, and certain sugars are trans­
formed first transformed into oligomers and monomers via hydrolysis in
subcritical water, while lignin contents remain unconverted. The use of
subcritical water as reaction medium during HTC has several benefits
over chemical reagents as it is environmentally-friendly, affordable, and
readily available. At high temperatures (>100 ◦ C), the hydrogen bonds
in water are weakened under pressure, leading to the generation of ionic
products (H + and OH − ), which catalyse the HTC reaction. Other re­
action mechanisms reported during the HTC process include
S. Fakudze and J. Chen Chemical Engineering Journal 457 (2023) 141004

Table 1 power generation plants, or as a precursor for value-added environ­

Operational challenges of common biomass and fossil-based feedstocks during mental materials.
combustion/co-combustion. Significant research has been conducted on the conversion of organic
Feedstock Examples Negative Operational Ref. wastes into eco-friendly solid fuels via hydrothermal carbonization. Park
inherent Challenges et al. (2018) studied the hydrothermal treatment of algal biomass to
properties produce hydrochar fuel at in the range of 180 to 270 ◦ C and a reaction
Household - Food waste, - High - Reduced [32,40] time of 1 h, and their results indicated that the HTC process led to
waste paper nitrogen heating values, enhanced carbon contents, high energy density, and reduced atomic O/
contents, hazardous
C and H/C ratios [59]. In another study, Ruksathamcharoen et al. (2019)
extremely flame,
high Equipment investigated the hydrothermal carbonization of empty fruit bunch to
moisture corrosion, NOx produce high-quality fuel pellets with increased energy yields and su­
contents, pollution perior mechanical strength [60]. The use of additional chemical re­
high agents, surfactants and metal catalysts has also been extensively studied
volatile
contents,
to achieve enhanced HTC performance and better results. For instance,
low energy Ma et al. (2021) used citric acid as chemical catalyst for the conversion
density of pomelo peels into environmentally-friendly solid fuel with relatively
Agricultural - Straw, fruit - High - Reduced [41–45] low residual ash contents [21]. The use of surfactants such as Tween80
and forest peel, wood moisture heating values,
was reportedly effective in enhancing the mass yield of hydrochars by
waste sawdust, contents, equipment
cotton waste, high corrosion, promoting the polycondensation of furfural intermediates in the liquid
corncob/ volatile slagging, poor phase [61]. In addition, HTC has also been widely explored for the
cornstalk, contents, combustion treatment of fossils including low-grade coal, PVC, and other plastic
bamboo high ash perfomance, wastes [62,63], leading to the reduction of pollutant-forming elements
waste, contents, toxic ash
(S and Cl) and toxic mineral contents. Hence, hydrothermal carboniza­
animal low energy contents,
manure density reduced heat tion remained a robust tool not only in improving fuel properties of
transfer organic feedstocks, but also reducing their negative impact on the
Coal/coal - Low-grade - Low - CO2 emission, [46,47] environment.
waste coal, ROM calorific anthropogenic
coal, coal value, high SOx and NO
waste, coal sulfur and pollution, 4. Feedstock pre-treatment via co-hydrothermal carbonization
slime nitrogen reduced boiler
contents, performance 4.1. Overview of co-hydrothermal carbonization
high ash
contents
Polymer/ - PVC, HDPE, - High - CO2 emission, [34,48]
Co-hydrothermal carbonization emerged as a low-cost and effective
plastic PP, rubber, chlorine soot formation, thermochemical process for the conversion of organic wastes into
waste leather levels, toxic HCl hydrochar and other value-added products. The main distinction be­
extremely emission, tween the standard HTC and co-HTC processes is that for co-HTC, two or
high Hazardous
more feedstocks are used, whereas in HTC, one feedstock material is
volatile flame
contents utilized. In recent years, the number of researchers looking into the co-
Energy crops - Miscanthus, - High - Nitrogen oxide [49,50] HTC of biomass-fossil blends increased significantly. Saba et al. (2017)
switchgrass moisture (NOx) evaluated the synergistic effects of coal and miscanthus during co-HTC,
contents, emissions, and further demonstrated that the process led not only to reduced sulfur
high reduced boiler
volatile performance,
and ash contents, but also maintained high energy contents [27]. The
contents, equipment formation of homogenous hydrochars was also observed as particles of
high corrosion, miscanthus-derived hydrochars lied on the surface of coal, suggesting
nitrogen slagging and that coal provided skeleton for the formation of hydrochars, hence the
contents, fouling
high hydrochar yield (see Table 2). According to Saqib et al. (2019), the
Inorganic
elements co-HTC of food waste and coal at 300 ℃ also led to hydrochars with
(K, Ca, P, higher mass and energy yields compared to unblended food waste
Fe, S and hydrochars. In addition, the co-HTC derived hydrochars also showed 53
Cl), low % less ash contents compared to unblended coal [64]. Recently, Fakudze
energy
density
et al. (2022) systematically investigated the co-hydrothermal processing
Water plants - Water - High - Hazardous [51,52] of high-sulfur coal and watermelon peel to achieve the desulfurization of
hyacinth, volatile flame, reduced coal, while also targeting the enhancement of fuel properties of both
algae contents, heating value, feedstocks [56]. Notably, the co-HTC derived hydrochars showed
high soot formation
improved combustion stability, reduced residual ash contents, and
moisture
contents, stronger synergistic effects compared to fuel blends of untreated coal
low energy and watermelon peel hydrochar.
density In recent years, the co-HTC of lignocellulosic biomass and polyvinyl
chloride also became a trending research topic, due to the rising con­
cerns over the emission of toxic, chlorine-based gases [24,68,70].
dehydration, decarboxylation, aromatization and polycondensation (see
Thanks to the high calorific values (10–20 MJ/kg), PVC can be sus­
Fig. 4), for which pre-treatment or drying of the feedstock waste is not a
tainably converted into carbon-rich biofuels for power generation. Xue
prerequisite. HTC is also attractive due to the method’s ability to remove
et al. (2022) investigated the fuel properties of hydrochars produced by
toxic organic molecules and residual micro-pollutants from the solid
the co-hydrothermal processing of polyvinyl chloride and straw powder,
material into the process water. The carbon-rich hydrochar, which is
and reported that synergistic effects led to increased HHV and energy
often characterized by high hydrophobicity and increased energy den­
yields [71]. An increase in the reaction temperature led to enhanced
sity, can be used as an alternative solid fuel for the replacement of coal in
dechlorination rates during the co-HTC of biomass/PVC blends, with an

4
S. Fakudze and J. Chen Chemical Engineering Journal 457 (2023) 141004

Fig. 2. Conceptual co-firing systems for electricity generation.

Fig. 3. Illustration of the hydrothermal carbonization process.

almost quantitative extraction of chlorine at higher temperatures. Xu
et al. (2021) used co-HTC to recover energy from cotton waste and PVC
at different blending ratios and reaction temperatures, and obtained
hydrochars with high HHVs, fuel ratios, and up to 90.79 % dechlori­
nation efficiency [61]. The authors further mentioned that synergistic
effects existed during the co-HTC of cotton waste and PVC, promoting
the carbonization degree and dechlorination efficiency. The co-
hydrothermal processing of water hyacinth and PVC was optimized
using the response surface method (RSM) to study the interactions be­
tween process parameters and further implement a reliable model for
predicting the fuel performance of product hydrochars [72]. Based on
statistical analysis, reaction temperature was the principal factor influ­
encing hydrochar dechlorination rate, higher heating value, mass and
yield, and energy consumption. In a previous study, Yao et al. (2018)
performed the co-HTC of bamboo and PVC waste to produce premium
solid fuel with high carbon contents, low chlorine contents and robust
combustion performance [25]. Since the degradation of cellulose occurs
at ~200 ℃, the co-treatment of lignocellulosic biomass and PVC could
accelerate the dechlorination of the latter due to the substitution of –Cl
with –OH, hence the improved dechlorination efficiency at temperatures

5
S. Fakudze and J. Chen
Fig. 4. Proposed co-HTC reaction mechanisms including dechlorination/desulfurization channels (Adapted from Xue et al. (2022) [71] and Xu et al. (2021) [75].
between 200 and 300 ℃. The enhanced carbonization rate was also
reportedly attributed to the formation of OH free radicals, acting as
catalyst for the remaining carbonization reactions [68]. Hence, the co-
HTC of biomass and fossils presented an eco-friendly and effective
approach for valorizing the two feedstocks into high-quality fuels.
4.2. Reaction mechanisms
Co-hydrothermal carbonization is an advanced thermochemical
process that involves a series of reaction mechanisms and pathways that
lead to the changes in chemical and structural compositions of product
chars. This section provides a detailed review of the HTC reaction
mechanisms of biomass-coal and biomass-PVC blends, focusing on the
main carbonization pathways and desulfurization/dechlorination pro­
cesses. Unlike other thermochemical methods such as direct co-
combustion and co-pyrolysis, co-HTC not only minimizes the release
of pollutants in gaseous form, but also eliminates the risk of auto-
ignition [70]. As the process is carried out in subcritical water, it in­
volves different reaction mechanisms, such as hydrolysis, dehydration,
decarboxylation, aromatization and condensation, some of which are
not present in other carbonization methods [55,56]. During the co-HTC
of biomass-fossil feedstocks, biomass-originated cellulose is degraded by
hydrolysis to form glucose, which is then converted into intermediates
of 5-HMF, acetic acid, and other intermediates [71]. Meanwhile,
hemicellulose is broken down by hydrolysis to form d-xylose, which
forms some furfurals/furans through dehydration [70]. As a complex
hydrocarbon polymer with aromatic constituents, dissolved lignin is
degraded into catechol and phenols by hydrolysis [73]. The process-
generated organic acids not only act as catalyst for the subsequent
carbonization reactions (i.e. condensation and aromatization), but also
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Chemical Engineering Journal 457 (2023) 141004
contribute to the removal of sulfur and chloride from the fossil-based
feedstocks [65,72]. The removal of chlorine is mainly supported by
free –OH ions from organic intermediates, which then substitute the Cl
ions in the vinyl chloride chains [68]. Through the catalysis effect of free
radicals, some chloride contents are also removed in the form of HCl and
chloroallylic structures, and this process is called the elimination reac­
tion [74]. In our previous study, the co-hydrothermal carbonization of
high sulfur coal with watermelon peel led to enhanced desulfurization
rates compared to individual HTC [56]. Thanks to the oxidative –OOH
from acetic acid, organic sulfur contents were transformed into sulfides,
sulfoxides and sulfates, which dissolve in the liquid phase, forming
sulfuric acid.
4.3. Fuel properties of co-HTC derived hydrochars
The physicochemical characteristics of hydrochar are usually
dependent on the reaction conditions (mainly temperature and time)
and the initial properties of the raw feedstocks, hence the importance of
research on the impact of these factors [76]. As explained in the previous
sections, during co-HTC, lignocellulosic components of biomass are
converted into carbon-rich hydrochar through a series of reaction
mechanisms, while the inorganic elements of fossil-based feedstocks are
released and dissolved in the process water, thus the improved hydro­
char fuel properties. In this review, the fuel properties of biomass-coal
and biomass-PVC feedstocks were rigorously analyzed based on the re­
sults of previous studies, as shown in Fig. 5 and Table 2. Amongst the
selected studies of biomass-coal co-HTC, hydrochar produced from the
co-treatment of food waste and coal (FW-coal) showed the lowest
moisture contents (3.7 %) [65], while that obtained from the fuel blend
of sewage sludge and coal slime (SS-coal) demonstrated the highest
S. Fakudze and J. Chen Chemical Engineering Journal 457 (2023) 141004

Table 2 depending on the specific biomass type [77,78]. As a synthetic polymer

Summary of literature related to co-hydrothermal carbonization of biomass and of vinyl chloride, which is classified as a volatile organic compound
fossil-based feedstocks. (VOC), untreated PVC is customarily characterized by extremely high
Feedstock Denotation Conditions Solvent HY Reference volatile contents (~95 %) [23,72]. Based on Fig. 5a and 5b, co-
(%) hydrothermal carbonization is effective in the reduction of volatiles in
Miscanthus MC-coal 200 ◦ C for Distilled 80.5 [27] both biomass-coal and biomass-PVC blends. Hydrochars produced via
and coal 0.5 h water the co-HTC of biomass and coal feedstocks had VM contents in the range
Rice straw and RS-coal 260 ◦ C for Distilled 50.4 [65] of 15.7 % to 39.5 %, except the MC-coal hydrochar which contained
run-of-mine 8h water
62.7 % of volatiles [27]. Remarkably, the volatile contents of hydrochars
coal 260 ◦ C for Acetic acid/ 61.2
6h hydrogen derived from the hydrothermal processing of biomass-PVC blends
peroxide ranged from 53.0 % to 73.2 %, indicating a significant difference from
220 ◦ C for KOH/ 59.8 the initial VM contents of untreated PVC. Obviously, the blending ratio
8h methanol played a huge role as biomass has lower VM contents compared to PVC,
Watermelon WP-coal 260 ◦ C for Distilled 81.1 [56]
peel and 3h water/
however, it is clear that the co-HTC process was also effective in con­
high-sulfur hydrogen verting the volatile contents. This can be proved by the enhanced fixed
coal peroxide carbon (FC) contents in co-HTC derived hydrochars. Biomass-PVC
Food waste FW-coal 300 ◦ C for Distilled 71.1 [64] blended hydrochars were characterized by FC contents between 24.2
and coal 1h water
and 43.2 %. The higher FC contents in bamboo-PVC (43.2 %) [25] and
Food waste FW-CW 230 ◦ C for Distilled 60.6 [66]
and coal 0.5 h water corncob-PVC (40.2 %) [24] hydrochars was mainly attributed to the
waste larger contents of lignin in both feedstocks, however, it has also been
Sewage sludge SS-coal 240 ◦ C for Sulfuric 81.0 [67] speculated that the porous structure of lignocellulosic biomass provides
and coal 2h acid a skeleton for the polycondensation of small molecular compounds,
slime
leading to the formation of secondary char (fixed carbon) [68]. Based on
Bamboo and BM-PVC 260 ◦
C for Distilled 41.2 [25]
PVC 1h water the reviewed studies, the FC contents of biomass-coal hydrochars varied
Pomelo peel PP-PVC 220 ◦
C for Citric acid 38.5 [68] from 33.1 % to 69.4 %, depending on the feedstock type, blending ratio,
and PVC 6h and processing conditions. Fakudze et al. (2022) [56] also attributed the
Cotton waste CW-PVC 260 C for Distilled 38.5 [69]
increment of FC contents in hydrochars prepared via the co-HTC of
◦

and PVC 2h water

Pinewood PS-PVC 280 ◦
C for Distilled 42.6 [70] watermelon peel (WP) and coal to the polycondensation mechanism
sawdust and 1h water reported by Paksung et al. (2020) [79]. During hydrothermal process­
PVC ing, biomass-originated natural polymers are first converted into
Corncob and CC-PVC 260 ◦ C for Citric acid 40.4 [24] furfural and 5-hydroxymethylfurfural (5-HMF) compounds by hydroly­
PVC 1h Distilled 42.2
sis. These small molecular compounds then form oligomers due to their
water
Sodium 41.8 reaction with α-carbonyl aldehydes in the process water, and finally
carbonate agglomerate into carbonaceous spheres, leading to an increase in fixed
Straw powder SP-PVC 240 ◦ C for Distilled 39.2 [71] carbon contents [79].
and PVC 2h water
Water WH-PVC 260 ◦ C for Distilled 39.88 [72] Fixed carbon(%)
hyacinth 1h water Fuel ratio = (1)
Volatile matter(%)
and PVC
In solid fuels, the ash content is also an important parameter in
evaluating their fuel performance and environmental impact during
moisture contents (37.5 %) [67]. Although hydrothermal processing has combustion, hence it is often extensively studied in biomass-fossil co-
the ability to improve the hydrophobicity of hydrochars, such is firing. The ash contents of hydrochars obtained from the hydrothermal
dependent on the feedstock type and operating conditions such as re­ carbonization of different biomass-coal and biomass-PVC fuel blends
action temperature and time, hence the difference in moisture contents. were compared based on the results of previous studies. Hydrochars
For biomass-PVC blends, the moisture contents of co-HTC derived derived from the co-HTC of food waste-coal [64] and miscanthus-coal
hydrochars ranged between 1.1 and 8.3 %, with the cotton textile waste [27] showed the lowest ash contents, which were 3.4 % and 3.7 %,
and PVC (CW-PVC) blend demonstrating the highest [69], and pomelo respectively. Meanwhile, the hydrochar blend of sewage sludge and coal
peel-PVC hydrochar (PP-PVC) showing the lowest moisture contents slime (SS-coal) demonstrated the highest ash contents (37.5 %) amongst
[68]. Nevertheless, the moisture contents of biomass-fossil based all biomass-coal blended hydrochars, which was highly attributed to the
hydrochars were within the limit of solid biofuel specifications (<10 %). abundance of incombustible mineral contents in sewage sludge [80].
Typically, untreated PVC is characterized by very low (0.05–0.10 %) According to Fan et al. (2020), sewage sludge is usually characterized by
moisture contents, making it an ideal solid feedstock for biofuel pro­ extremely high ash contents (50–75 %) due to mineral particles (Si, Al,
duction [62]. The increase in hydrophobicity can be attributed to the Fe, P, Ca, Mg and others) entrapped during biological treatment [81].
dehydration mechanism which leads to reduced hydroxyl groups when Remarkably, biomass-PVC hydrochars showed very low ash contents in
the reaction temperature is elevated. Although most studies do not place the range of 1.1 % to 8.3 %, owing to the VOC nature of polyvinyl
an emphasis on the moisture contents of product hydrochars, the min­ chloride. Hence, it terms of residual ash formation, biomass-PVC
imal moisture levels of co-HTC derived hydrochars could play a major hydrochars can be considered more environmentally-friendly. The fuel
role in reducing energy consumption from extensive drying processes. ratio (FR) is a standard index used to evaluate the fuel performance of
Volatile matter (VM) is one of the most critical parameters in the solid fuels. FR is calculated as a mass ratio of fixed carbon to volatile
characterization of solid fuels, hence it is part of the standard proximate matter [82], where a higher value indicates better fuel performance.
analysis. Generally, untreated coal is characterized by lower volatile Fig. 5c and 5d show the FR values of hydrochars produced via the co-
contents compared to raw biomass and polyvinyl chloride. According to HTC of various biomass-coal and biomass-PVC blends, respectively.
previous studies, untreated bituminous coal [27], coal slime [30] and Based on the results of the selected studies, hydrochars prepared by the
ROM coals [65] had VM contents of 34.3 %, 20.7 % and 29.7 %, co-HTC of watermelon peel and high-sulfur coal (WP-coal) had the
respectively. On the contrary, untreated biomass feedstocks were usu­ highest fuel ratio (4.42), while that produced from the fuel blended of
ally accompanied by volatile contents in the range of 35–60 %, miscanthus and coal had the lowest (0.52). Biomass-PVC hydrochars

7
S. Fakudze and J. Chen Chemical Engineering Journal 457 (2023) 141004

Fig. 5. Proximate analysis and fuel ratios of biomass/coal hydrochars (a, c) and biomass/PVC hydrochars (b, d).

exhibited lower fuel ratios in the range of 0.33 to 0.83, which was due to
the abundance of volatile contents in polyvinyl chloride. According to
Fakudze et al. (2022) [56], the fuel ratio of blended fuels can be
enhanced by adding catalytic reagents such as citric acid, acetic acid,
and other organic acids, which accelerate hydrothermal reactions such
as dehydration, decarboxylation and polycondensation, leading to an
increase in fixed carbon contents.
The ultimate analysis, carbon retention rate, higher heating value
and energy yield of a fuel are often investigated to provide a broad
understanding of its combustion characteristics. Elemental parameters
such as carbon (C), oxygen (O), hydrogen (H), nitrogen (N) and sulfur
(S) provide an estimate of the fuel performance during combustion,
including the heat output and gas emissions. In this review, the
elemental compositions of co-HTC derived hydrochars from the selected
studies of biomass-fossil feedstocks were summarized in Table 3. The
carbon contents of biomass-coal hydrochars ranged between 49.5 and
81.2 %, with food waste-coal hydrochar having the highest C contents,
and food waste-coal waste (FW-CW) exhibiting the lowest. Although the
carbon contents of fuel blends are usually affected by operating condi­
tions such as reaction temperature, time and solvent type; the carbon
contents of product hydrochars is largely dependent on the initial values
of untreated feedstocks. For instance, in the case of rice straw and ROM

Table 3
Fuel properties of hydrochars produced via co-hydrothermal carbonization of various biomass and fossil-based feedstocks under different process conditions.
Feedstock Ultimate analysis (%) CR (%) HHV (MJ/kg) EY (%) Reference

C H O N

MC-coal 58.2 5.3 34.4 0.8 83.3 24.8 84.6 [27]

RS-coal 74.4 4.4 8.4 1.2 79.0 30.1 81.2 [65]
WP-coal 70.9 3.3 9.8 0.3 99.5 29.0 94.7 [56]
FW-coal 81.2 3.1 14.4 0.9 101.7 28.6 82.1 [64]
FW-CW 49.5 4.5 14.8 1.9 103.6 23.0 71.3 [66]
SS-coal 43.0 3.1 12.7 2.0 83.6 16.7 84.0 [67]
BM-PVC 71.0 5.9 13.7 0.2 69.0 32.2 60.9 [25]
PP-PVC 60.9 4.4 32.4 0.7 57.6 22.6 51.8 [68]
CW-PVC 63.4 5.6 20.1 0.2 75.3 30.7 84.1 [69]
PS-PVC 74.3 5.8 16.0 / 71.3 30.9 / [70]
CC-PVC 76.3 6.4 11.8 0.2 76.6 32.8 75.4 [24]
SP-PVC 70.4 5.9 13.5 0.7 45.0 27.6 54.1 [71]
WH-PVC 73.8 6.6 14.1 0.4 64.5 33.0 74.0 [72]

8
S. Fakudze and J. Chen
coal (RS-coal), the original C contents untreated coal and rice straw were
63.8 % and 43.2 %, respectively, hence by calculation based on the
blending ratio (7:3), the untreated fuel blend had C contents of ~57.6 %.
Therefore, it can be assumed that the hydrothermal process contributed
an additional 16.5 % to the initial carbon contents of the blend. Biomass-
PVC hydrochars also demonstrated relatively high carbon contents
ranging from 60.9 % to 76.3 %, owing to the bulky carbon polymer
chains of polyvinyl chloride [37]. During HTC, the macromolecular
network of vinyl chloride is broken down by reaction mechanisms such
as hydrolysis, dehydration, decarboxylation, aromatization, and dehy­
drochlorination to form short-chain hydrocarbons [62], hence the in­
crease in carbon contents. In addition to C contents, hydrochar fuel
typically contains certain amounts of oxygen elements, mainly origi­
nating from volatile organic compounds. As demonstrated in Table 3,
hydrochars prepared via the co-hydrothermal treatment of biomass-coal
blends exhibited oxygen contents in the range of 8.4–14.8 %, except the
miscanthus-coal blend, which was highly due to the miscanthus-
originated volatile compounds. Hydrochars derived via the co-HTC of
biomass and PVC demonstrated O contents of 11.8–32.4 %, attributed to
the high volatile components in the initial feedstocks, especially poly-
vinyl chloride. According to Johansson et al. (2021), solid fuel-
contained oxygen can be helpful in enhancing the reactivity and
combustibility of a fuel, however it is usually associated with heavy soot
formation [83].
In Table 3, it can be noted that all biomass-fossil based hydrochars
showed nitrogen contents of < 1.0 %, except the fuel blends of sewage
sludge-coal (2.0 %), food waste-coal waste (1.9 %), and rice straw-ROM
coal (1.2 %). Both sewage sludge (up to 10 %) and food waste are usually
accompanied by very high N contents due to the abundance of protein
compounds [84]. Generally, solid fuel-contained nitrogen contents are
associated with the formation of nitrogen oxides (NOx) during com­
bustion. From the results of Mazumder et al. (2020) and Yang et al.
(2020), it can be seen that co-hydrothermal processing was effective in
reducing the N contents of the fuel blends [66,67]. The atomic ratios O/
C and H/C are usually used to characterize the carbonization degree of
hydrochar fuel. Generally, lower values of O/C and H/C atomic ratios
indicate a higher degree of carbonization or better fuel properties closer
to lignite and anthracite. In most studies, the O/C and H/C ratios of
different samples are often plotted against each other in a Van Krevelen
diagram as shown in Fig. 6. In the diagram, it can been observed that
most biomass-fossil hydrochars shifted towards the position of after co-
HTC, both biomass-coal and biomass-PVC blends shifted towards the
position of coal (between peat and anthracite), which proved the
Fig. 6. Van Krevelen diagram of atomic ratios for various biomass-fossil hydrochars [27,56,65,64,66,67,25,68,69,70,24,71,72].
9
Chemical Engineering Journal 457 (2023) 141004
enhancement of fuel properties due to the dehydration and decarbox­
ylation reactions.
C contenthydrochar
CR(%) = HY × (2)
C contentfeedstock
HHV hydrochar
EY(%) = HY × (3)
HHV feedstock
The carbon retention (CR), higher heating value (HHV) and energy yield
(EY) are also key indicators in the characterization of solid fuels and
have been extensively analyzed in many studies to assess the fuel per­
formance of product chars. CR is defined as the percentage yield of
carbon retained in the product hydrochar after hydrothermal process­
ing, calculated by Eq. (2). Based on the results of previous studies, the
CR of biomass-coal hydrochars was remarkably high (79.0–103.6 %),
suggesting that the co-HTC process not only retained the carbon con­
tents, but also slightly increased them. Hydrochars derived from the co-
hydrothermal treatment of biomass and PVC exhibited CR values vary­
ing from 45.0 to 75.3 %, which was mainly due to the extraction of water
soluble organic compounds into the process water, such as furfural and
5-hydroxymethylfurfural (5-HMF). The higher heating values of
biomass-coal hydrochars assessed in this review were in the range of
23.0 to 30.1 MJ/kg, with the fuel blend of rice straw and ROM coal
reported by Fakudze et al. (2021) showing the highest HHV, which was
mainly due to the catalysis effect of the acetic acid used as a solvent
during the experiment [65]. Interestingly, hydrochars prepared via the
co-HTC of biomass and PVC demonstrated much higher HHVs, with BM-
PVC, CC-PVC, and WH-PVC characterized by higher heating values of
32.2, 32.8 and 33.0 MJ/kg, respectively. The energy yield, calculated by
Eq. (3), is defined as the energy content of product hydrochars retained
after hydrothermal carbonization on the basis of mass yield and HHV. As
shown on Table 3, biomass-coal hydrochars were characterized by EY
values of 71.3 % to 94.7 %, while biomass-PVC had energy yields in the
range of 51.8–84.1 %. Compared to the traditional HTC approach, the
co-hydrothermal processing of biomass with fossils resulted in superior
energy yields, owing to the enhanced repolymerization (agglomeration)
of biomass-based molecular compounds on the surface of fossils.
4.4. Effect of reaction temperature and time
As mentioned in previous sections, process conditions such as reac­
tion temperature, residence time, blending ratio and solvent type are
influential to the fuel properties of co-HTC derived hydrochars. Over
S. Fakudze and J. Chen
recent years, several studies have critically investigated the effect of
these parameters on the product hydrochars of biomass-fossil blends. In
this section, the influence of the co-HTC reaction temperature and time
on performance indicators such as hydrochar yield, fuel ratio, carbon
retention, and energy yield was rigorously examined using data ob­
tained from previous studies on the co-treatment of biomass and fossils.
As illustrated in Fig. 7, the highest HY value (75.9–81.2 %) was observed
at a reaction temperature of ~260 ◦ C and reaction time of between 3 and
4 h. For the fuel ratio, the best result was observed between 230 and
240 ◦ C and reaction time of 1.5–2.5 h, also owing to the efficient
degradation of cellulose and hemicellulose at this temperature range. In
Fig. 7c, the effect of co-HTC conditions on the carbon retention is shown,
and it can be observed that highest CR value is produced under a tem­
perature of ~260 ◦ C and 3–5 h reaction time. However, according to the
graph, it can also be concluded that the carbon retention increases with
an increase in temperature and time. Similarly, the energy yield also
increased with reaction temperature and time, with higher EY values
observed between 260 and 300 ◦ C and 3 to 6 h. Notably, the influence of
these process parameters on the fuel properties may also vary depending
on the biomass feedstock type. For instance, several authors reported a
gradual decrease in both hydrochar yield and energy yield as the reac­
tion temperature and time increased [70], which is because of the pro­
cess water-dissolved hydrocarbon compounds. Meanwhile, due to the
significant increase in HHV, the energy yield of some blended hydro­
chars could be enhanced at higher temperatures [27]. Hence the
importance of comprehensive reviews such as this one, to fully under­
stand the different responses of various feedstocks to co-HTC conditions.
Fig. 7. Effect of temperature and reaction time on a) hydrochar
[27,56,65,64,66,67,25,68,69,70,24,71,72].
10
Chemical Engineering Journal 457 (2023) 141004
5. Synergistic effects
Due to robust interactions between biomass and fossil derived sub­
stances during co-processing, many studies reported synergies in the co-
HTC of biomass-coal and biomass-PVC feedstocks. The synergistic ef­
fects could be attributed to a chain of reaction mechanisms that occur
during the hydrothermal process, leading to enhanced fuel properties
such as higher carbon contents, fixed carbon, hydrochar yield, and en­
ergy yields. In the present review, the synergistic effects of co-HTC
derived biomass-fossil hydrochars were evaluated using Eq. (4) to
explore the influence of reaction temperature and blending ratio
(biomass proportion) on the process synergy.
Xexp − Xcal
SE(%) = × 100% (4)
Xcal
Xcal = αηbiomass + βηfossil (5)
where Xexp and Xcal represents the experimental and calculated values of
different performance indicators such as hydrochar yield, carbon con­
tents, and fixed carbon. α and β refer to the weight proportions of
biomass and fossil feedstocks in the blend, respectively. ηbiomass and ηfossil
represent the performance indicator (i.e. HY, C contents, FC) corre­
sponding to the non-mixed biomass-based and fossil-based hydrochars.
Fig. 8 shows the contour plots of the synergistic effects of biomass-coal
and biomass-PVC hydrochars based on hydrochar yield, carbon contents
and fixed carbon. Based on the analysis, hydrochars synthesized via the
co-treatment of biomass and coal showed the strongest synergy
(55.3–74.2 %) under the reaction temperature of 250–280 ◦ C and a
yield, b) fuel ratio, c) carbon retention rate, d) energy yield
S. Fakudze and J. Chen
Fig. 8. Contour plots of co-HTC synergistic effects based on a) hydrochar yield, b) carbon contents, and c) fixed carbon for biomass-coal [27,56,65,64,66,67] and
biomass-PVC hydrochars [25,68,69,70,24,71,72].
biomass proportion of ~50 %. According to Saba et al. (2017) hydro­
chars prepared with 50 wt% coal and 50 wt% miscanthus showed pos­
itive synergistic effects at 260 ◦ C, owing to the formation of organic
acids from biomass during hydrothermal processing. These acids are
speculated to serve as catalysts for further carbonization reactions
including dehydration, decarboxylation and repolymerization. Fakudze
et al. (2022) added that the coal surface also provides a skeleton for the
agglomeration of smaller carbon compounds [56], leading to the for­
mation of secondary char or pseudo-lignin, hence the better hydrochar
11
Chemical Engineering Journal 457 (2023) 141004
yield. For biomass-PVC hydrochars, the region with the strongest syn­
ergistic effects (2.26–2.73) based on HY was observed at 220–250 ◦ C
with a biomass proportion of 45 % to 65 %.
On the basis of carbon contents, the synergistic effects of biomass-
coal hydrochars were strongly dependent on the biomass proportion,
with the strongest synergy observed under a biomass proportion of ~70
%. Meanwhile, for biomass-PVC blends, the synergistic effects were not
dependent on the blending ratio, but were rather more influenced by the
temperature, with strongest synergistic effect observed at 220 ◦ C and
S. Fakudze and J. Chen
260 ◦ C. Note-worthily, in the center region (i.e. 240 ◦ C, 50 % biomass),
an anti-synergistic effect (negative synergy) was observed between
biomass and PVC during co-HTC, which could be attributed to the
dissolution of smaller molecular compounds in the liquid filtrate. As an
important property of solid fuels, the synergistic effects of hydrochars
produced by co-HTC were also evaluated based on fixed carbon con­
tents. In Fig. 8c, it can be observed that the synergy of biomass-coal
blends increased with an increase in biomass proportion, while for
biomass-PVC hydrochars the strongest synergistic effects was found at
~220 ◦ C under the blending ratio of 50 % biomass to 50 % PVC. Hence,
for biomass-PVC blends it can be concluded that the blending ratio of 5:5
is more optimal for the realization of synergistic effects during co-HTC.
For biomass-coal, the optimal conditions vary with the different per­
formance indicators (i.e. hydrochar yield, carbon contents, fixed carbon,
etc.), thus there should consideration of the desired fuel properties prior
to the optimization of co-HTC conditions. Several authors also reported
the presence of synergistic effects during the combustion of hydrochars
produced through co-hydrothermal carbonization. The corresponding
synergistic/anti-synergistic effect during the combustion of blended
hydrochars is generally evaluated using the weight loss data obtained by
thermogravimetric analysis (TGA). According to Song et al. (2019) [85]
and Yang et al (2020) [86], a synergistic effect is observed when the
deviation between experimental weight loss curve and calculated
weight loss curve is positive, while an anti-synergistic effect can be
observed when the deviation is negative. The presence of synergistic
effects during the combustion of biomass-fossil hydrochars is reportedly
attributed to the active ●OH free radicals from hydroxyl and carbonyl
groups, acting as catalysts to accelerate the combustion of char [6,56].
6. Environmental and economic benefits
6.1. Environmental benefits of co-hydrothermal processing
Co-hydrothermal carbonization has the potential to limit environ­
mental challenges related to waste biomass as it emits less pollutant
substances compared to other waste management methods such as
incineration, landfilling, and composting. As discussed in previous sec­
tions, depending on the process conditions, the co-hydrothermal pro­
cessing of biomass and fossil-based feedstocks enables the extraction of
inorganic substances such as toxic minerals, sulfur and chloride con­
tents, thus air pollution could be avoided by the co-HTC process. Several
studies investigated the migration of mechanisms of pollutant elements
such as sulfur and chlorine during hydrothermal carbonization [87–89].
Wu et al. (2015) studied the transformation of sulfur during the hy­
drothermal processing of low rank coal, and reported that the contents
of organic sulfur showed a significant decrease, while sulfate contents
increased gradually after the process [90]. The formation of sulfates and
sulfur-containing gases (such as SO2) was mainly attributed to the
decomposition of water-soluble aliphatic sulfur, while some proportions
of thiophenic sulfur in the process water were generated from water-
soluble sulfones and sulfoxides at high temperatures (≥160 ◦ C). In a
different study, Wang et al. (2022) reported an almost similar mecha­
nism for the migration and transformation of sulfur from sewage sludge
[87]. Therefore, it can be concluded that hydrothermal carbonization
presents an effective approach for the removal of sulfur from organic
wastes, also minimizing the release of odorous sulfur-containing gases.
To better assess the environmental impact of the co-HTC, the
desulfurization and dechlorination efficiencies (DE) of biomass-coal and
biomass-PVC feedstocks were evaluated using elemental analysis data
obtained from the previous studies as shown in Eq. (6):
Yfs − Yhc
DE(%) = × 100% (6)
Yfs
where Yfs represents the sulfur/chlorine contents in the feedstock blend,
calculated based on blending ratio, and Yhc is the sulfur/chlorine
12
Chemical Engineering Journal 457 (2023) 141004
content of co-HTC derived hydrochars. The desulfurization and
dechlorination rates of different feedstock combinations are shown in
Fig. 9. According to Saha et al. (2021), coal-contained sulfur is usually in
the form of sulfates, pyrite and organic sulfur, and it is generally
extracted through leaching as sulfoxides, sulfones, and sulfates [30].
Reaction temperature and solvent type (alkali or acid) are the two
crucial factors that influence the sulfur transformation during hydro­
thermal processing. The desulfurization of low rank coal via by acid/
alkali chemical solvents is a traditional method first report in the 1990 s
[91], however it has been significantly enhanced through advanced
techniques such as microwave, ultrasound and hydrothermal process­
ing. Potassium oxide and acetic acid remained two of the most common
alkali and acid solvents for coal desulfurization, respectively. Interest­
ingly, organic acids such as acetic acid and formic acid are some of the
major by-products of lignocellulosic biomass during HTC, which is due
to the hydrolysis and dehydration of natural polymers (cellulose and
hemicellulose) and other simple compounds in the presence of subcrit­
ical water. Hence, the enhanced desulfurization rates during the co-HTC
of biomass-coal blends (Fig. 9a) could be attributed to the elimination of
sulfur by the catalytic effect of these organic acids. Worth-noting,
hydrochar derived from the co-treatment of sewage sludge and coal
slime showed negative desulfurization efficiency (− 8.1 %), which was
highly due to the significant concentration of sulphur (2.3 wt%) in
sewage sludge, combined with the use of sulfuric acid as a solvent during
HTC [67]. Remarkably, the desulfurization efficiency of other biomass-
coal hydrochars ranged from 47.8 % to 100 %, with RS-coal exhibiting
the highest DE value. Although the dechlorination mechanism is
different, the co-HTC of biomass and chlorinated polymer wastes also
proved as an effective technique for reducing Cl contents in the blends.
Based on Fig. 9b, biomass-PVC hydrochars from the reported studies
demonstrated excellent dechlorination efficiencies in the range of 80.0
% to 96.2 %. Ma et al. (2019) investigated the evolution of chlorine
during hydrothermal carbonization of medical waste mainly consisting
of PVC, and discovered that the substitution of Cl elements by biomass-
originating –OH groups accounted for a major part of the dechlorination
mechanism [89]. According to Zhao et al. (2022), other contents of Cl
are removed by the elimination reaction, which starts with the genera­
tion of free radicals, and then chloroallylic structures and HCl, which is
subsequently removed to form polyenes [74]. Wei et al. (2022) exam­
ined the chloride contents of process water obtained from the co-HTC of
pomelo peel and PVC, and found that large quantities of the removed Cl
was present in the liquid phase in the form of hydrochloric acid and
other chlorinated compounds [68]. Even though no significant study has
been reported yet, the chlorinated and sulfur-containing intermediates
in liquid phase could be recovered by further processing to reduce the
toxicity of the process water. Hence, there is still a need for further
research into the recovery of sulfur and chlorine contents from process
water to improve the eco-friendliness of the co-HTC of biomass and
fossil-based feedstocks.
Several authors also reported that hydrothermal processing can also
lead to the migration of heavy metals [92]. According Qi et al. (2022),
due to the degradation of organic components, heavy metals such as
such as Cu, Cr and Ni were left exposed on the hydrochar surface, which
led to an increase in the weight ratio of these elements in the product
hydrochars [92]. Ke et al. (2021) studied the transformation of heavy
metals during the hydrothermal carbonization of PVC, and reported that
the concentrations of Cd, Pb and Zn were significantly reduced through
HTC, whereas Cr and Ni were enriched in the product hydrochar [93]. In
a previous study, Xiang et al. (2017) [94] also reported that the HTC of
lignite coal could effectively reduce heavy metals (such as Hg, As, Se),
owing to the thermal degradation of coal and dissolution of organic
intermediates into the process water. However, it was worth-noting that
hydrothermal carbonization reduced the bioavailability of heavy metals
and enhanced their stability during combustion. As a result, heavy
metals contained in the hydrochar could act only as catalysts for the
combustion reaction, and remain in the residual ash after combustion,
S. Fakudze and J. Chen
Fig. 9. A)Desulfurization [56,27,65,67,64] and b) dechlorination efficiencies [25,68,69,71,24] of co-HTC derived hydrochars.
hence reducing the potential ecological risk of the hydrochars in terms
of air pollution. On the other hand, some elements such as Arsenic (As)
and some alkali metals are reportedly leached and dissolved in the liquid
phase, reducing the amount of ash-forming elements in the product
hydrochars [92], and therefore, preventing the accumulation of ash
from the combustion process.
Thanks to the abundance of organic acids (acetic acid, formic acid
and glycolic acid), the remaining process water can be recirculated
within the reactor multiple times to catalyze the HTC reaction and
improve efficiency. According to Wei et al. (2022), process water
retrieved after the co-HTC of pomelo peel and PVC contained up to 31.1
% of organic acids, including formic acid (8.1 %), acetic acid (13.4 %),
aminocaproic acid (2.5 %), and others. Previous studies showed that the
recirculation of HTC process water not only dramatically improved fuel
properties, but also minimized the negative impacts of the process to­
wards the environment [95,96]. Li et al. (2022) studied the effect of
recirculating process water during the hydrothermal carbonization of
PVC and agricultural wastes for solid fuel production, and reported that
this approach resulted in high chloride removal and improved energy
recovery efficiencies [97]. Although there is currently a lack of studies
that examined the recirculation of process water during the co-HTC of
biomass and coal, Kahilu et al. (2021) reported that process water ob­
tained after the co-HTC of sewage sludge and coal was rich in organic
intermediates and elements such as Ca, Si, Ni, Mg, Cd, and Cr, owing to
the degradation of the organic structure by process-generated acids,
which led to the leaching and dissolution of inorganic contaminants into
the liquid phase [98]. Therefore, the recirculation of process water
provides a promising co-HTC approach as it prevents water wastage,
reduces negative environmental impacts, and enhances hydrochar fuel
properties.
6.2. Economic benefits of co-hydrothermal processing
As a single-pot and wet-treatment approach, co-hydrothermal
carbonization is undoubtedly a low-cost and energy-efficient approach
for the valorization of multiple feedstocks. The most significant advan­
tage of co-HTC is that it allows the treatment of feedstocks with high
moisture contents without pre-drying, which greatly reduces energy
consumption and operational costs [99]. Therefore, a wide variety of
feedstocks, including agricultural residues, industrial wastes, animal
manure and aquatic biomass are suitable for hydrothermal carboniza­
tion. In HTC processing, most electrical costs come from reactor feed
pumping, reactor heating and pelletization. However, since standard
coal-fired boilers do not require pelletization, the co-treatment of
biomass and fossil-based feedstocks could further reduce operational
costs [66]. Since the process is carried out under subcritical water, the
ionic products (H + and OH − ) act as catalysts during the process, hence
13
Chemical Engineering Journal 457 (2023) 141004
eliminating the need for higher temperatures [100]. In general, treat­
ment in the range 180 to 250 ◦C produces an adequate higher heating
value (HHV) without the need for excess energy input. Furthermore,
since hydrochar is more hydrophobic compared to pyrolysis derived
biochar, the co-HTC process allows for reduced drying costs prior to
combustion. Saba et al. (2019) estimated the cost of electricity for
producing hydrochar via co-hydrothermal carbonization to be approx­
imately $46 per MWh− 1, which is nearly twice the fuel costs of standard
coal-fired plants [101]. Meanwhile, Mazumder et al. (2020) reported
that the costs of hydrochar production via co-HTC was between $55 to
$65 per ton of hydrochar, with the reactor system, pumping system,
water utility costs, heat recovery costs, filtration and dewatering costs,
and storage accounting for 55.19 %, 22.81 %, 3.10 %, 6.57 %, 7.78 %,
and 3.77 %, respectively [66]. The estimated break-even selling price
was in the range of $60 to $69 due to costs of transportation and raw
materials. However, further sensitivity analysis showed that using large
scale HTC reactors could reduce the production costs. In addition, more
economic benefits could be realized through the valorization of co-HTC
by-products, especially the organic compound rich process water. For
instance, in our previous work [56], the liquid filtrate obtained from the
co-HTC of low-grade coal and watermelon peels demonstrated an
abundance of aldehydes, esters, alcohols, ketones and some organic
acids. There is still a need for further investigation of the operational
costs related to the co-HTC of biomass-coal and biomass-PVC blends to
better evaluate the economic benefits of the process at industrial scale.
However, based on the above discussion it is obvious that co-
hydrothermal treatment could present more environmental and eco­
nomic benefits compared to other thermochemical methods.
7. Future perspectives and insights
Based on the results discussed above, co-hydrothermal carbonization
is a promising approach for the valorization of biomass-fossil blends into
cleaner solid fuels with excellent fuel properties and reduced negative
impacts to the environment. Although the hydrothermal processing
technology has been widely applied in biomass conversion, there is still
a limit in the number of studies that investigated the co-treatment of
biomass with fossil feedstocks such as low rank coal, coal waste and
PVC. Specifically, there is still lack of understanding on the reaction
mechanisms that take place during the co-HTC of biomass-coal blends.
Therefore, there is an urgent need for further systematical research to
provide insights on the complex reaction mechanisms that lead to the
enhanced fuel properties and reduced sulfur/chlorine contents. This can
be achieved by conducting a comprehensive experimental study using
various biomass-fossil feedstock combinations under different co-HTC
conditions (temperature, time, blending ratio, solvent type). Then, the
obtained data can be used to develop a standard mathematical model to
S. Fakudze and J. Chen
provide an understanding of the transformations that occur during co-
HTC. Since the findings of the studies reviewed in this paper showed
that different process conditions tend to result in hydrochars with
varying properties, such information could be useful in optimizing co-
HTC conditions according to the desired fuel properties of hydrochars.
Besides, this sort of information is very critical in the design of industrial
reactors, and providing insights on the environmental and economic
aspects of the co-HTC process.
Further, a framework for the molecular dynamics of biomass and
coal (or PVC) particles can be developed for the visualization of their
interactions during co-hydrothermal treatment. Although this may be a
challenge, it should be considered as several studies have previously
explored the simulation of molecular interactions for the standard HTC
of lignocellulosic biomass [102,103]. The simulation of molecular dy­
namics based on the reactive force field (ReaxFF) has proved effective in
providing an understanding of the hydrothermal reaction mechanisms
of biomass polymer compounds such as cellulose and hemicellulose,
under supercritical water and other green solvents. Despite these prog­
ress, the simulation of molecular dynamics for biomass-fossil blends is
yet to be explored, which is mainly due to the fact that the reaction paths
for individual biomass feedstocks is quite complicated, and vary
depending on the feedstock type. Nevertheless, it is highly recom­
mended for future studies to consider the implementation of computa­
tional simulations to fundamentally understand the co-HTC reaction
mechanisms. As previous studies reported the presence of synergistic
effects during co-HTC, the development of mathematical models and
molecular dynamic simulations could provide further insight on the
origin of this synergy.
As a thermochemical process, hydrothermal carbonization relies on
constant heating and high pressure, hence evaluating the energy effi­
ciency or balance of the co-HTC process is very crucial. However, at
present, the number of literatures that assessed the energy balance and
economic viability of co-HTC is still limited. A techno-economic study
provides an understanding of the energy and economic aspects of the co-
hydrothermal carbonization, which are two of the most critical factors in
the commercialization phase. In any case, the energy balance of
hydrochar production should consider the total energy required for the
HTC process, including any pre-processing techniques, which is then
deducted from the total energy generated by the product hydrochars
[104]. Notably, an attempt was made by Mazumder et al. (2020) to
examine the techno-economic aspects of producing hydrochar via the
co-hydrothermal processing of food waste and coal waste [66]. Based on
their findings, transportation and raw material acquisition were major
contributors of the hydrochar production costs.
In addition, future studies should take into consideration the utili­
zation of the co-HTC liquid filtrate, which is usually characterized by
large quantities of organic compounds. It has been noted that previous
studies disregarded this potentially valuable process water, yet it could
be further valorized into liquid biofuel or other value-added green
chemicals. Previously, Wei et al. (2022) reported that the process water
derived from the co-HTC of pomelo peel and PVC demonstrated an
abundance of 5-Hydroxymethylfurfural, acetic acid, formic acid, 2-Prop­
anone, and some hydroxyl and carbonyl compounds [68], suggesting
that it could be used as a precursor in green chemistry. Another prom­
ising approach for the utilization of process water is through its recir­
culation or reuse in further cycles of the of the co-hydrothermal
carbonization process, however it has not yet been reported in the co-
treatment of biomass-fossil blends. The recirculation of this acid-rich
liquid filtrate could help enhance the carbonization process, while also
reducing the environmental impact of the co-HTC process, especially
downstream water pollution related issues [96,105].
8. Conclusions
The co-treatment of biomass and fossil-based feedstocks is gradually
receiving growing attention, owing to the wide-application of co-firing
14
Chemical Engineering Journal 457 (2023) 141004
as an effective approach for reducing CO2 emissions from the energy
industry. Co-hydrothermal carbonization emerged as a promising tech­
nique for the pre-treatment of biomass-coal and biomass-PVC blends to
improve their fuel properties, while also targeting the reduction of sulfur
or chlorine contents. This low-cost and eco-friendly approach has
proved to be highly effective in the conversion of biomass-fossil blends
into carbon-rich solid fuels. In consideration of these attractive features,
this critical review assessed and analyzed a selection of research works
focused on the co-hydrothermal carbonization of biomass-coal and
biomass-PVC blends for the first time. The studies reviewed herein
include experimental works on the production of hydrochar from rice
straw-coal, miscanthus-coal, corncob-PVC, bamboo-PVC, and other
feedstock combinations. To understand the influence of co-HTC condi­
tions on the hydrochar properties, special focus was paid on the
hydrochar yield, energy yield, carbon retention and fuel ratio. Addi­
tionally, an emphasis was placed on the relationship between process
conditions (reaction temperature, time and biomass proportion) and
synergistic effects during co-HTC. Finally, the environmental benefits of
co-treating biomass and fossils were assessed based on the desulfuriza­
tion and dechlorination efficiencies.
According to the findings of previous works, hydrochars derived via
the co-HTC of biomass and fossil feedstocks demonstrated enhanced fuel
properties, with increased carbon contents, HHVs and energy yields. The
research works reviewed in this paper also revealed that co-
hydrothermal carbonization can effectively improve the hydrochar
yield, owing to the repolymerization of smaller molecular compounds
into pseudo lignin or secondary char. Moreover, the co-HTC of biomass-
coal and biomass-PVC blends led to improved desulfurization and
dechlorination efficiencies, respectively. Meanwhile, biomass-coal
hydrochars showed a significant reduction in ash contents, hence sug­
gesting that co-hydrothermal carbonization is not only cost-effective,
but could also improve the environmental-friendliness of fuel blends.
In addition, the results showed that the co-HTC of biomass-fossil blends
is accompanied synergistic effects, which are mainly dependent on the
reaction temperature and blending ratio. However, it is recommended
for future studies to systematically investigate the origin of these syn­
ergistic effects, specifically the reaction mechanisms behind them, to
provide a complete understanding and pave the way for future research.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
The authors do not have permission to share data.
Acknowledgement
This work was supported by the Qing Lan Project of Jiangsu Province
and the Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD).
References
[1] H. Wang, Y. Tian, X. Chen, J. Li, Kinetic and synergetic effect analysis of the co-
combustion of coal blended with polyurethane materials, ACS Omega 5 (40)
(2020) 26005–26014, https://doi.org/10.1021/acsomega.0c03449.
[2] Z. Xue, Z. Zhong, X. Lai, Investigation on gaseous pollutants emissions during co-
combustion of coal and wheat straw in a fluidized bed combustor, Chemosphere
240 (2020), 124853, https://doi.org/10.1016/j.chemosphere.2019.124853.
[3] T. Kober, H.W. Schiffer, M. Densing, E. Panos, Global energy perspectives to 2060
– WEC’s world energy scenarios 2019, Energy Strategy Rev. 31 (2020), 100523,
https://doi.org/10.1016/j.esr.2020.100523.
[4] R. Millati, R.B. Cahyono, T. Ariyanto, I.N. Azzahrani, R.U. Putri, M.
J. Taherzadeh, Agricultural, industrial, municipal, and forest wastes: an
S. Fakudze and J. Chen
overview, in: M.J. Taherzadeh, K. Bolton, J. Wong, A. Pandey (Eds.), Sustainable
Resource Recovery and Zero Waste Approaches, Elsevier, 2019, pp. 1–22.
[5] T.A. Khan, A.S. Saud, S.S. Jamari, M.H.A. Rahim, J.-W. Park, H.-J. Kim,
Hydrothermal carbonization of lignocellulosic biomass for carbon rich material
preparation: a review, Biomass Bioenerg. 130 (2019), 105384, https://doi.org/
10.1016/j.biombioe.2019.105384.
[6] S. Onenc, S. Retschitzegger, N. Evic, N. Kienzl, J. Yanik, Characteristics and
synergistic effects of co-combustion of carbonaceous wastes with coal, Waste
Manag. 71 (2018) 192–199, https://doi.org/10.1016/j.wasman.2017.10.041.
[7] T. Wang, Q. Yang, Y. Wang, J. Wang, Y. Zhang, W.P. Pan, Arsenic release and
transformation in co-combustion of biomass and coal: effect of mineral elements
and volatile matter in biomass, Bioresour. Technol. (2019), 122388, https://doi.
org/10.1016/j.biortech.2019.122388.
[8] F. Güleç, L.M.G. Riesco, O. Williams, E.T. Kostas, A. Samson, E. Lester,
Hydrothermal conversion of different lignocellulosic biomass feedstocks – effect
of the process conditions on hydrochar structures, Fuel 302 (2021), 121166,
https://doi.org/10.1016/j.fuel.2021.121166.
[9] S. Xin, F. Huang, X. Liu, T. Mi, Q. Xu, Torrefaction of herbal medicine wastes:
characterization of the physicochemical properties and combustion behaviors,
Bioresour. Technol. 287 (2019), 121408, https://doi.org/10.1016/j.
biortech.2019.121408.
[10] H. Pawlak-Kruczek, L. Niedzwiecki, M. Sieradzka, A. Mlonka-Mędrala,
M. Baranowski, M. Serafin-Tkaczuk, A. Magdziarz, Hydrothermal carbonization
of agricultural and municipal solid waste digestates – structure and energetic
properties of the solid products, Fuel 275 (2020), 117837, https://doi.org/
10.1016/j.fuel.2020.117837.
[11] S. Seyedsadr, R. Al Afif, C. Pfeifer, Hydrothermal carbonization of agricultural
residues: a case study of the farm residues -based biogas plants, Carbon Resour,
Convers. 1 (1) (2018) 81–85, https://doi.org/10.1016/j.crcon.2018.06.001.
[12] G. Wang, J. Zhang, J.-Y. Lee, X. Mao, L. Ye, W. Xu, X. Ning, N. Zhang, H. Teng,
C. Wang, Hydrothermal carbonization of maize straw for hydrochar production
and its injection for blast furnace, Appl. Energy 266 (2020), 114818, https://doi.
org/10.1016/j.apenergy.2020.114818.
[13] C. Deng, R. Lin, X. Kang, B. Wu, X. Ning, D. Wall, J.D. Murphy, Co-production of
hydrochar, levulinic acid and value-added chemicals by microwave-assisted
hydrothermal carbonization of seaweed, Chem. Eng. J. 441 (2022), 135915,
https://doi.org/10.1016/j.cej.2022.135915.
[14] C. Nzediegwu, M.A. Naeth, S.X. Chang, Carbonization temperature and feedstock
type interactively affect chemical, fuel, and surface properties of hydrochars,
Bioresour. Technol. 330 (2021), 124976, https://doi.org/10.1016/j.
biortech.2021.124976.
[15] T. Wang, Y. Zhai, H. Li, Y. Zhu, S. Li, C. Peng, B. Wang, Z. Wang, Y. Xi, S. Wang,
C. Li, Co-hydrothermal carbonization of food waste-woody biomass blend
towards biofuel pellets production, Bioresour. Technol. 267 (2018) 371–377,
https://doi.org/10.1016/j.biortech.2018.07.059.
[16] J.-B. Xiong, Z.-Q. Pan, X.-F. Xiao, H.-J. Huang, F.-Y. Lai, J.-X. Wang, S.-W. Chen,
Study on the hydrothermal carbonization of swine manure: The effect of process
parameters on the yield/properties of hydrochar and process water, J. Anal. Appl.
Pyrolysis 144 (2019), 104692, https://doi.org/10.1016/j.jaap.2019.104692.
[17] C. Deng, X. Kang, R. Lin, J.D. Murphy, Microwave assisted low-temperature
hydrothermal treatment of solid anaerobic digestate for optimising hydrochar
and energy recovery, Chem. Eng. J. 395 (2020), 124999, https://doi.org/
10.1016/j.cej.2020.124999.
[18] Y. Wang, L. Qiu, M. Zhu, G. Sun, T. Zhang, K. Kang, Comparative evaluation of
hydrothermal carbonization and low temperature pyrolysis of eucommia
ulmoides oliver for the production of solid biofuel, Sci. 9 (1) (2019) 5535,
https://doi.org/10.1038/s41598-019-38849-4.
[19] Y. Zhang, I. Zahid, A. Danial, J. Minaret, Y. Cao, A. Dutta, Hydrothermal
carbonization of miscanthus: processing, properties, and synergistic Co-
combustion with lignite, Energy 225 (2021), 120200, https://doi.org/10.1016/j.
energy.2021.120200.
[20] E. Atallah, J. Zeaiter, M.N. Ahmad, J.J. Leahy, W. Kwapinski, Hydrothermal
carbonization of spent mushroom compost waste compared against torrefaction
and pyrolysis, Fuel Process. Technol. 216 (2021), 106795, https://doi.org/
10.1016/j.fuproc.2021.106795.
[21] R. Ma, S. Fakudze, Q. Shang, Y. Wei, J. Chen, C. Liu, J. Han, Q. Chu, Catalytic
hydrothermal carbonization of pomelo peel for enhanced combustibility of coal/
hydrochar blends and reduced CO2 emission, Fuel 304 (2021), 121422, https://
doi.org/10.1016/j.fuel.2021.121422.
[22] B. Babinszki, E. Jakab, Z. Sebestyén, M. Blazsó, B. Berényi, J. Kumar, B.
B. Krishna, T. Bhaskar, Z. Czégény, Comparison of hydrothermal carbonization
and torrefaction of azolla biomass: analysis of the solid products, J. Anal. Appl.
Pyrolysis 149 (2020), 104844, https://doi.org/10.1016/j.jaap.2020.104844.
[23] N. Huang, P. Zhao, S. Ghosh, A. Fedyukhind, Co-hydrothermal carbonization of
polyvinyl chloride and moist biomass to remove chlorine and inorganics for clean
fuel production, Appl. Energy 240 (2019) 882–892, https://doi.org/10.1016/j.
apenergy.2019.02.050.
[24] X. Lu, X. Ma, X. Chen, Z. Yao, C. Zhang, Co-hydrothermal carbonization of
polyvinyl chloride and corncob for clean solid fuel production, Bioresour.
Technol. 301 (2020), 122763, https://doi.org/10.1016/j.biortech.2020.122763.
[25] Z. Yao, X. Ma, Characteristics of co-hydrothermal carbonization on polyvinyl
chloride wastes with bamboo, Bioresour. Technol. 247 (2018) 302–309, https://
doi.org/10.1016/j.biortech.2017.09.098.
[26] Q. Lang, B. Zhang, Z. Liu, Z. Chen, Y. Xia, D. Li, J. Ma, C. Gai, Co-hydrothermal
carbonization of corn stalk and swine manure: combustion behavior of hydrochar
15
Chemical Engineering Journal 457 (2023) 141004
by thermogravimetric analysis, Bioresour. Technol. 271 (2019) 75–83, https://
doi.org/10.1016/j.biortech.2018.09.100.
[27] A. Saba, P. Saha, M.T. Reza, Co-hydrothermal carbonization of coal-biomass
blend: influence of temperature on solid fuel properties, Fuel Process. Technol.
167 (2017) 711–720, https://doi.org/10.1016/j.fuproc.2017.08.016.
[28] Y.-H. Li, H.-T. Lin, K.-L. Xiao, J. Lasek, Combustion behavior of coal pellets
blended with Miscanthus biochar, Energy 163 (2018) 180–190, https://doi.org/
10.1016/j.energy.2018.08.117.
[29] J. Koornneef, M. Junginger, A. Faaij, Development of fluidized bed
combustion—an overview of trends, performance and cost, Prog. Energy
Combust. Sci. 33 (1) (2007) 19–55, https://doi.org/10.1016/j.pecs.2006.07.001.
[30] L. Xinjie, Z. Shihong, W. Xincheng, S. Jinai, Z. Xiong, W. Xianhua, Y. Haiping,
C. Hanping, Co-combustion of wheat straw and camphor wood with coal slime:
thermal behaviour, kinetics, and gaseous pollutant emission characteristics,
Energy 234 (2021), 121292, https://doi.org/10.1016/j.energy.2021.121292.
[31] A. Kazagic, N. Hodzic, S. Metovic, Co-combustion of low-rank coal with woody
biomass and miscanthus: an experimental study, Energies 11 (3) (2018) 601,
https://doi.org/10.3390/en11030601.
[32] J.S. Chae, S.W. Kim, J.H. Lee, J.C. Joo, T.I. Ohm, Combustion characteristics of
solid refuse fuel derived from mixture of food and plastic wastes, J. Mater. Cycles
Waste Manag. 22 (4) (2020) 1047–1055, https://doi.org/10.1007/s10163-020-
00996-6.
[33] Q. Wang, G. Wang, J. Zhang, J.-Y. Lee, H. Wang, C. Wang, Combustion behaviors
and kinetics analysis of coal, biomass and plastic, Thermochim. Acta 669 (2018)
140–148, https://doi.org/10.1016/j.tca.2018.09.016.
[34] Y. Tang, X. Ma, Z. Lai, Y. Fan, Thermogravimetric analyses of co-combustion of
plastic, rubber, leather in N2/O2 and CO2/O2 atmospheres, Energy 90 (2015)
1066–1074, https://doi.org/10.1016/j.energy.2015.08.015.
[35] Y. Takeshita, K. Kato, K. Takahashi, Y. Sato, S. Nishi, Basic study on treatment of
waste polyvinyl chloride plastics by hydrothermal decomposition in subcritical
and supercritical regions, J. Supercrit. Fluids 31 (2004) 185–193, https://doi.
org/10.1016/j.supflu.2003.10.006.
[36] A. Buekens, K. Cen, Waste incineration, PVC, and dioxins, J. Mater. Cycles Waste
Manag. 13 (3) (2011) 190–197, https://doi.org/10.1007/s10163-011-0018-9.
[37] Z. Yao, X. Ma, A new approach to transforming PVC waste into energy via
combined hydrothermal carbonization and fast pyrolysis, Energy 141 (2017)
1156–1165, https://doi.org/10.1016/j.energy.2017.10.008.
[38] W.-H. Chen, B.-J. Lin, Y.-Y. Lin, Y.-S. Chu, A.T. Ubando, P.L. Show, et al., Progress
in biomass torrefaction: principles, applications and challenges, Prog. Energy
Combust. Sci. 82 (2021), 100887, https://doi.org/10.1016/j.pecs.2020.100887.
[39] Y. Niu, H. Tan, S.E. Hui, Ash-related issues during biomass combustion: Alkali-
induced slagging, silicate melt-induced slagging (ash fusion), agglomeration,
corrosion, ash utilization, and related countermeasures, Prog. Energy Combust.
Sci. 52 (2016) 1–61, https://doi.org/10.1016/j.pecs.2015.09.003.
[40] J. Wielinski, C. Müller, A. Voegelin, E. Morgenroth, R. Kaegi, Combustion of
sewage sludge: kinetics and speciation of the combustible, Energy Fuels 32 (10)
(2018) 10656–10667, https://doi.org/10.1021/acs.energyfuels.8b02106.
[41] A. Kanca, Investigation on pyrolysis and combustion characteristics of low quality
lignite, cotton waste, and their blends by TGA-FTIR, Fuel 263 (2020), 116517,
https://doi.org/10.1016/j.fuel.2019.116517.
[42] Z. Sun, B. Jin, M. Zhang, R. Liu, Y. Zhang, Experimental studies on cotton stalk
combustion in a fluidized bed, Energy 33 (8) (2008) 1224–1232, https://doi.org/
10.1016/j.energy.2008.04.002.
[43] M. Stasiak, M. Molenda, M. Bańda, J. Wiącek, P. Parafiniuk, E. Gondek,
Mechanical and combustion properties of sawdust—straw pellets blended in
different proportions, Fuel Process. Technol. 156 (2017) 366–375, https://doi.
org/10.1016/j.fuproc.2016.09.021.
[44] Q. Ren, C. Zhao, L. Duan, X. Chen, NO formation during agricultural straw
combustion, Bioresour. Technol. 102 (14) (2011) 7211–7217, https://doi.org/
10.1016/j.biortech.2011.04.090.
[45] J.A. Siles, F. Vargas, M.C. Gutierrez, A.F. Chica, M.A. Martin, Integral valorisation
of waste orange peel using combustion, biomethanisation and co-composting
technologies, Bioresour. Technol. 211 (2016) 173–182, https://doi.org/10.1016/
j.biortech.2016.03.056.
[46] C. Martin, M. Villamanan, C. Chamorro, J. Otero, A. Cabanillas, J. Segovia, Low-
grade coal and biomass co-combustion on fluidized bed: exergy analysis, Energy
31 (2–3) (2006) 330–344, https://doi.org/10.1016/j.energy.2005.01.008.
[47] M. Onifade, B. Genc, Spontaneous combustion of coals and coal-shales, Int. J.
Min. Sci. Technol. 28 (6) (2018) 933–940, https://doi.org/10.1016/j.
ijmst.2018.05.013.
[48] Y. Miyake, M. Tokumura, Q. Wang, T. Amagai, Y. Horii, K. Kannan, Mechanism of
formation of chlorinated pyrene during combustion of polyvinyl chloride,
Environ. Sci. Technol. 51 (24) (2017) 14100–14106, https://doi.org/10.1021/
acs.est.7b04854.
[49] Y. Wang, Y. Shao, M.D. Matovic, J.K. Whalen, Exploring switchgrass and
hardwood combustion on excess air and ash fouling/slagging potential:
Laboratory combustion test and thermogravimetric kinetic analysis, Energy
Convers. Manag. 97 (2015) 409–419, https://doi.org/10.1016/j.
enconman.2015.03.070.
[50] X.C. Baxter, L.I. Darvell, J.M. Jones, T. Barraclough, N.E. Yates, I. Shield,
Miscanthus combustion properties and variations with Miscanthus agronomy,
Fuel 117 (2014) 851–869, https://doi.org/10.1016/j.fuel.2013.09.003.
[51] H. Yue, Y. Rao, J. Meng, X. Zhang, R. Chen, Gas emissions from combustion of
water hyacinth and pistia stratiotes biomass particles under O2/CO2, Energy
Source, Part A (2020) 1–15, https://doi.org/10.1080/15567036.2020.1843568.
S. Fakudze and J. Chen
[52] H. Huang, J. Liu, H. Liu, J. Hu, F. Evrendilek, Dynamic insights into combustion
drivers and responses of water hyacinth: evolved gas and ash analyses, J. Clean.
Prod. 276 (2020), 124156, https://doi.org/10.1016/j.jclepro.2020.124156.
[53] L. Chen, C. Wen, W. Wang, T. Liu, E. Liu, H. Liu, Z. Li, Combustion behaviour of
biochars thermally pretreated via torrefaction, slow pyrolysis, or hydrothermal
carbonisation and co-fired with pulverised coal, Renew. Energy 161 (2020)
867–877, https://doi.org/10.1016/j.renene.2020.06.148.
[54] F.R. Vieira, C.M. Romero Luna, G.L.A.F. Arce, I. Ávila, Optimization of slow
pyrolysis process parameters using a fixed bed reactor for biochar yield from rice
husk, Biomass Bioenerg. 132 (2020), 105412, https://doi.org/10.1016/j.
biombioe.2019.105412.
[55] H. Merdun, Z.B. Laougé, A.S. Çığgın, Synergistic effects on co-pyrolysis and co-
combustion of sludge and coal investigated by thermogravimetric analysis,
J. Therm. Anal. Calorim. 146 (2021) 2623–2637, https://doi.org/10.1007/
s10973-021-10608-6.
[56] S. Fakudze, Y. Wei, P. Zhou, J. Han, J. Chen, Synergistic effects of process-
generated organic acids during co-hydrothermal carbonization of watermelon
peel and high-sulfur coal, J. Environ. Chem. Eng. 10 (2022), 107519, https://doi.
org/10.1016/j.jece.2022.107519.
[57] S. Zhang, X. Zhu, S. Zhou, H. Shang, J. Luo, Hydrothermal carbonization for
hydrochar production and its application, in: Y.S. Ok, D.C.W. Tsang, N. Bolan, J.
M. Novak (Eds.), Biochar From Biomass and Waste, Elsevier, 2019, pp. 275–295.
[58] L. Zaccariello, D. Battaglia, B. Morrone, M.L. Mastellone, Hydrothermal
Carbonization: A Pilot-Scale Reactor Design for Bio-waste and Sludge Pre-
treatment, Waste Biomass Valorization 13 (9) (2022) 3865–3876, https://doi.
org/10.1007/s12649-022-01859-x.
[59] K.Y. Park, K. Lee, D. Kim, Characterized hydrochar of algal biomass for producing
solid fuel through hydrothermal carbonization, Bioresour. Technol. 258 (2018)
119–124, https://doi.org/10.1016/j.biortech.2018.03.003.
[60] S. Ruksathamcharoen, T. Chuenyam, P. Stratong-on, H. Hosoda, L. Ding,
K. Yoshikawa, Effects of hydrothermal treatment and pelletizing temperature on
the mechanical properties of empty fruit bunch pellets, Appl. Energy 251 (2019),
113385, https://doi.org/10.1016/j.apenergy.2019.113385.
[61] Z. Xu, R. Qi, M. Xiong, D. Zhang, H. Gu, W. Chen, Conversion of cotton textile
waste to clean solid fuel via surfactant-assisted hydrothermal carbonization:
Mechanisms and combustion behaviors, Bioresour. Technol. 321 (2021), 124450,
https://doi.org/10.1016/j.biortech.2020.124450.
[62] J. Poerschmann, B. Weiner, S. Woszidlo, R. Koehler, F.D. Kopinke, Hydrothermal
carbonization of poly(vinyl chloride), Chemosphere 119 (2015) 682–689,
https://doi.org/10.1016/j.chemosphere.2014.07.058.
[63] D. Zhang, P. Liu, X. Lu, L. Wang, T. Pan, Upgrading of low rank coal by
hydrothermal treatment: coal tar yield during pyrolysis, Fuel Process. Technol.
141 (2016) 117–122, https://doi.org/10.1016/j.fuproc.2015.06.037.
[64] N. Ul Saqib, A.K. Sarmah, S. Baroutian, Effect of temperature on the fuel
properties of food waste and coal blend treated under co-hydrothermal
carbonization, Waste Manag. 89 (2019) 236–246, https://doi.org/10.1016/j.
wasman.2019.04.005.
[65] S. Fakudze, Y. Wei, Q. Shang, R. Ma, Y.-H. Li, J. Chen, P. Zhou, J. Han, C. Liu,
Single-pot upgrading of run-of-mine coal and rice straw via Taguchi-optimized
hydrothermal treatment: fuel properties and synergistic effects, Energy 236
(2021), 121482, https://doi.org/10.1016/j.energy.2021.121482.
[66] S. Mazumder, P. Saha, K. McGaughy, A. Saba, M.T. Reza, Technoeconomic
analysis of co-hydrothermal carbonization of coal waste and food waste, Biomass
Convers. Biorefin. 12 (1) (2020) 39–49, https://doi.org/10.1007/s13399-020-
00817-8.
[67] X. Yang, B. Wang, X. Song, F. Yang, F. Cheng, Co-hydrothermal carbonization of
sewage sludge and coal slime with sulfuric acid for N, S doped hydrochar,
J. Clean. Prod. 354 (2022), 131615, https://doi.org/10.1016/j.
jclepro.2022.131615.
[68] Y. Wei, S. Fakudze, Y. Zhang, R. Ma, Q. Shang, J. Chen, C. Liu, Q. Chu, Co-
hydrothermal carbonization of pomelo peel and PVC for production of hydrochar
pellets with enhanced fuel properties and dechlorination, Energy 239 (2022),
122350, https://doi.org/10.1016/j.energy.2021.122350.
[69] Z. Xu, R. Qi, D. Zhang, Y. Gao, M. Xiong, W. Chen, Co-hydrothermal
carbonization of cotton textile waste and polyvinyl chloride waste for the
production of solid fuel: Interaction mechanisms and combustion behaviors,
J. Clean. Prod. 316 (2021), 128306, https://doi.org/10.1016/j.
jclepro.2021.128306.
[70] X. Zhang, L. Zhang, A. Li, Co-hydrothermal carbonization of lignocellulosic
biomass and waste polyvinyl chloride for high-quality solid fuel production:
hydrochar properties and its combustion and pyrolysis behaviors, Bioresour.
Technol. 294 (2019), 122113, https://doi.org/10.1016/j.biortech.2019.122113.
[71] Y. Xue, L. Bai, M. Chi, X. Xu, Z. Chen, K. Yu, Z. Liu, Co-hydrothermal
carbonization of pretreatment lignocellulose biomass and polyvinyl chloride for
clean solid fuel production: hydrochar properties and its formation mechanism,
J. Environ. Chem. Eng. 10 (1) (2022), 106975, https://doi.org/10.1016/j.
jece.2021.106975.
[72] C. Zhang, X. Ma, T. Huang, Y. Zhou, Y. Tian, Co-hydrothermal carbonization of
water hyacinth and polyvinyl chloride: Optimization of process parameters and
characterization of hydrochar, Bioresour. Technol. 314 (2020), 123676, https://
doi.org/10.1016/j.biortech.2020.123676.
[73] Y. Xu, Y. Liu, Y. Bu, M. Chen, L. Wang, Review on the ionic liquids affecting the
desulfurization of coal by chemical agents, J. Clean. Prod. 284 (2021), 124788,
https://doi.org/10.1016/j.jclepro.2020.124788.
[74] A. Sahoo, K. Saini, M. Jindal, T. Bhaskar, K.K. Pant, Co-Hydrothermal
Liquefaction of algal and lignocellulosic biomass: status and perspectives,
16
Chemical Engineering Journal 457 (2023) 141004
Bioresour. Technol. 342 (2021), 125948, https://doi.org/10.1016/j.
biortech.2021.125948.
[75] Y. Zhao, G. Jia, Y. Shang, P. Zhao, X. Cui, Q. Guo, Chlorine migration during
hydrothermal carbonization of recycled paper wastes and fuel performance of
hydrochar, Process Saf. Environ. Prot. 158 (2022) 495–502, https://doi.org/
10.1016/j.psep.2021.12.041.
[76] S. Mazumder, P. Saha, M.T. Reza, Co-hydrothermal carbonization of coal waste
and food waste: fuel characteristics, Biomass Convers. Biorefin. (2020) 1–11,
https://doi.org/10.1007/s13399-020-00771-5.
[77] R. Garcia, C. Pizarro, A.G. Lavin, J.L. Bueno, Biomass proximate analysis using
thermogravimetry, Bioresour. Technol. 139 (2013) 1–4, https://doi.org/
10.1016/j.biortech.2013.03.197.
[78] R.J. Stirling, C.E. Snape, W. Meredith, The impact of hydrothermal carbonisation
on the char reactivity of biomass, Fuel Process. Technol. 177 (2018) 152–158,
https://doi.org/10.1016/j.fuproc.2018.04.023.
[79] N. Paksung, J. Pfersich, P.J. Arauzo, D. Jung, A. Kruse, Structural effects of
cellulose on hydrolysis and carbonization behavior during hydrothermal
treatment, ACS Omega 5 (21) (2020) 12210–12223, https://doi.org/10.1021/
acsomega.0c00737.
[80] A.S. Oliveira, A. Sarrión, J.A. Baeza, E. Diaz, L. Calvo, A.F. Mohedano, M.
A. Gilarranz, Integration of hydrothermal carbonization and aqueous phase
reforming for energy recovery from sewage sludge, Chem. Eng. J. 442 (2022),
136301, https://doi.org/10.1016/j.cej.2022.136301.
[81] J. Fan, Y. Li, H. Yu, Y. Li, Q. Yuan, H. Xiao, F. Li, B. Pan, Using sewage sludge with
high ash content for biochar production and Cu(II) sorption, Sci. Total Env. 713
(2020), 136663, https://doi.org/10.1016/j.scitotenv.2020.136663.
[82] P.J. Arauzo, M. Atienza-Martínez, J. Ábrego, M.P. Olszewski, Z. Cao, A. Kruse,
Combustion characteristics of hydrochar and pyrochar derived from digested
sewage sludge, Energies 13 (16) (2020) 4164, https://doi.org/10.3390/
en13164164.
[83] A.-C. Johansson, R. Molinder, T. Vikström, H. Wiinikka, Particle formation during
suspension combustion of different biomass powders and their fast pyrolysis bio-
oils and biochars, Fuel Process. Technol. 218 (2021), 106868, https://doi.org/
10.1016/j.fuproc.2021.106868.
[84] S. Corrado, C. Caldeira, G. Carmona-Garcia, I. Körner, A. Leip, S. Sala, Unveiling
the potential for an efficient use of nitrogen along the food supply and
consumption chain, Glob. Food Sec. 25 (2020), 100368, https://doi.org/
10.1016/j.gfs.2020.100368.
[85] Y. Song, H. Zhan, X. Zhuang, X. Yin, C. Wu, Synergistic Characteristics and
Capabilities of Co-hydrothermal Carbonization of Sewage Sludge/Lignite
Mixtures, Energy Fuels 33 (9) (2019) 8735–8745, https://doi.org/10.1021/acs.
energyfuels.9b01766.
[86] G. Yang, X. Jia, Y. Zhao, X. Huo, C. Song, Z. Zhang, Synergistic analysis of co-
combustion of sunflower straw and coal gangue, Bioresources 15 (4) (2020)
7770–7779, https://doi.org/10.15376/biores.15.4.7770-7779.
[87] Z. Wang, J. Huang, W. Hu, D. Xie, M. Xu, Y. Qiao, In-depth study of the sulfur
migration and transformation during hydrothermal carbonization of sewage
sludge, Proc. Combust. Inst. (2022), https://doi.org/10.1016/j.
proci.2022.07.184.
[88] P. Saha, N. Saha, S. Mazumder, M.T. Reza, Transformation of sulfur during co-
hydrothermal carbonization of coal waste and food waste, Energies 14 (8) (2021)
2271, https://doi.org/10.3390/en14082271.
[89] D. Ma, Q. Feng, B. Chen, X. Cheng, K. Chen, J. Li, Insight into chlorine evolution
during hydrothermal carbonization of medical waste model, J. Hazard. Mater.
380 (2019), 120847, https://doi.org/10.1016/j.jhazmat.2019.120847.
[90] J. Wu, J. Liu, S. Yuan, X. Zhang, Y. Liu, Z. Wang, J. Zhou, Sulfur transformation
during hydrothermal dewatering of low rank coal, Energy Fuels 29 (10) (2015)
6586–6592, https://doi.org/10.1021/acs.energyfuels.5b01258.
[91] S.R. Palmer, E.J. Hippo, X.A. Dorai, Chemical coal cleaning with selective
oxidation, Fuel 73 (2) (1994) 161–169, https://doi.org/10.1016/0016-2361(94)
90109-0.
[92] X. Qi, X. Ma, Z. Yu, X. Lu, S. Liang, W. Teng, Addition of water hyacinth and
attapulgite during hydrothermal carbonization of sewage sludge: Migration
behavior of heavy metals and fuel characteristics of hydrochar, J. Environ. Chem.
Eng. 10 (6) (2022), 108857, https://doi.org/10.1016/j.jece.2022.108857.
[93] C. Ke, X. Ma, W. Zheng, L. Chen, Y. Tang, The volatilization of heavy metals
during combustion of polyvinyl chloride after hydrothermal carbonization,
J. Clean. Prod. 285 (2021), 124825, https://doi.org/10.1016/j.
jclepro.2020.124825.
[94] F. Xiang, Y. He, S. Kumar, Z. Wang, L. Liu, Z. Huang, J. Liu, K. Cen, Influence of
hydrothermal dewatering on trace element transfer in Yimin coal, Appl. Therm.
Eng. 117 (2017) 675–681, https://doi.org/10.1016/j.
applthermaleng.2016.12.100.
[95] H.S. Kambo, J. Minaret, A. Dutta, Process Water from the Hydrothermal
Carbonization of Biomass: A Waste or a Valuable Product? Waste Biomass
Valorization 9 (7) (2017) 1181–1189, https://doi.org/10.1007/s12649-017-
9914-0.
[96] H.B. Sharma, S. Panigrahi, K.R. Vanapalli, V.R.S. Cheela, S. Venna, B. Dubey,
Study on the process wastewater reuse and valorisation during hydrothermal co-
carbonization of food and yard waste, Sci. Total Env. 806 (2022), 150748,
https://doi.org/10.1016/j.scitotenv.2021.150748.
[97] Z. Li, S. Niu, J. Liu, Y. Wang, Solid fuel production from co-hydrothermal
carbonization of polyvinyl chloride and corncob: Higher dechlorination efficiency
and process water recycling, Sci. Total Environ. 843 (2022), 157082, https://doi.
org/10.1016/j.scitotenv.2022.157082.
S. Fakudze and J. Chen
[98] G.M. Kahilu, S. Bada, J. Mulopo, Physicochemical, structural analysis of coal
discards (and sewage sludge) (co)-HTC derived biochar for a sustainable carbon
economy and evaluation of the liquid by-product, Sci. 12 (1) (2022) 17532,
https://doi.org/10.1038/s41598-022-22528-y.
[99] X. Zhuang, J. Liu, Q. Zhang, C. Wang, H. Zhan, L. Ma, A review on the utilization
of industrial biowaste via hydrothermal carbonization, Renew. Sust. Energ. Rev.
154 (2022), 111877, https://doi.org/10.1016/j.rser.2021.111877.
[100] T. Ahmed Khan, H.J. Kim, A. Gupta, S.S. Jamari, R. Jose, Synthesis and
characterization of carbon microspheres from rubber wood by hydrothermal
carbonization, J. Chem. Technol. Biotechnol. 94 (5) (2018) 1374–1383, https://
doi.org/10.1002/jctb.5867.
[101] A. Saba, K. McGaughy, M. Reza, Techno-economic assessment of co-hydrothermal
carbonization of a coal-miscanthus blend, Energies 12 (4) (2019) 630, https://
doi.org/10.3390/en12040630.
17
Chemical Engineering Journal 457 (2023) 141004
[102] S.C. Rismiller, M.M. Groves, M. Meng, Y. Dong, J. Lin, Water assisted liquefaction
of lignocellulose biomass by ReaxFF based molecular dynamic simulations, Fuel
215 (2018) 835–843, https://doi.org/10.1016/j.fuel.2017.11.108.
[103] H. Jin, W. Ding, B. Bai, C. Cao, Molecular dynamics simulation study used in
systems with supercritical water, Rev. Chem. Eng. 38 (1) (2022) 95–109, https://
doi.org/10.1515/revce-2019-0068.
[104] C. Aragon-Briceño, A. Pożarlik, E. Bramer, G. Brem, S. Wang, Y. Wen, W. Yang,
H. Pawlak-Kruczek, Ł. Niedźwiecki, A. Urbanowska, K. Mościcki, M. Płoszczyca,
Integration of hydrothermal carbonization treatment for water and energy
recovery from organic fraction of municipal solid waste digestate, Renew. Energy
184 (2022) 577–591, https://doi.org/10.1016/j.renene.2021.11.106.
[105] J. Stemann, A. Putschew, F. Ziegler, Hydrothermal carbonization: process water
characterization and effects of water recirculation, Bioresour. Technol. 143
(2013) 139–146, https://doi.org/10.1016/j.biortech.2013.05.098.