energies

Review
A Review of Hydrothermal Liquefaction of Biomass for
Biofuels Production with a Special Focus on the Effect of
Process Parameters, Co-Solvents, and Extraction Solvents
Ankit Mathanker 1 , Snehlata Das 1 , Deepak Pudasainee 1 , Monir Khan 1 , Amit Kumar 2 and Rajender Gupta 1, *

1 Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 2R3, Canada;
mathanke@ualberta.ca (A.M.); snehlata@ualberta.ca (S.D.); pudasain@ualberta.ca (D.P.);
mmkhan@ualberta.ca (M.K.)
2 Department of Mechanical Engineering, University of Alberta, Edmonton, AB T6G 2R3, Canada;
amit.kumar@ualberta.ca
* Correspondence: rajender.gupta@ualberta.ca

Abstract: Hydrothermal liquefaction is one of the common thermochemical conversion methods

adapted to convert high-water content biomass feedstocks to biofuels and many other valuable
industrial chemicals. The hydrothermal process is broadly classified into carbonization, liquefaction,
and gasification with hydrothermal liquefaction conducted in the intermediate temperature range of
250–374 ◦ C and pressure of 4–25 MPa. Due to the ease of adaptability, there has been considerable
research into the process on using various types of biomass feedstocks. Over the years, various
solvents and co-solvents have been used as mediums of conversion, to promote easy decomposition



of the lignocellulosic components in biomass. The product separation process, to obtain the final


products, typically involves multiple extraction and evaporation steps, which greatly depend on the
Citation: Mathanker, A.; Das, S.;
type of extractive solvents and process parameters. In general, the main aim of the hydrothermal
Pudasainee, D.; Khan, M.; Kumar, A.;
process is to produce a primary product, such as bio-oil, biochar, gases, or industrial chemicals,
Gupta, R. A Review of Hydrothermal
such as adhesives, benzene, toluene, and xylene. All of the secondary products become part of
Liquefaction of Biomass for Biofuels
Production with a Special Focus on
the side streams. The optimum process parameters are obtained to improve the yield and quality
the Effect of Process Parameters, of the primary products. A great deal of the process depends on understanding the underlined
Co-Solvents, and Extraction Solvents. reaction chemistry during the process. Therefore, this article reviews the major works conducted
Energies 2021, 14, 4916. in the field of hydrothermal liquefaction in order to understand the mechanism of lignocellulosic
https://doi.org/10.3390/en14164916 conversion, describing the concept of a batch and a continuous process with the most recent state-of-
art technologies in the field. Further, the article provides detailed insight into the effects of various
Academic Editor: Sergio Ulgiati process parameters, co-solvents, and extraction solvents, and their effects on the products’ yield
and quality. It also provides information about possible applications of products obtained through
Received: 5 July 2021
liquefaction. Lastly, it addresses gaps in research and provides suggestions for future studies.
Accepted: 5 August 2021
Published: 11 August 2021
Keywords: biomass; biofuels; bio-oil; bio-crude; char; hydrothermal liquefaction; hydrothermal
processing; lignocellulosic biomass
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1. Introduction
In the recent past, our dependence on technology and energy needs has increased
significantly, either in the form of energy consumption for personal use, household pur-
Copyright: © 2021 by the authors.
poses, transportation, or agricultural needs. Most of this energy demand is met from fossil
Licensee MDPI, Basel, Switzerland.
fuels such as coal, petroleum, and natural gas. The excessive use of fossil fuels results in
This article is an open access article
increased emissions of oxides of nitrogen, sulfur, mercury, and other trace elements, which
distributed under the terms and are very harmful to human health and vegetation. Apart from these emissions, the use
conditions of the Creative Commons of fossil fuels results in greenhouse gas emissions leading to global warming and drastic
Attribution (CC BY) license (https:// climate changes [1]. The depletion of fossil fuels was one of the prominent issues, but now
creativecommons.org/licenses/by/ the environment is a much larger concern, forcing researchers to investigate alternative
4.0/). renewable and sustainable sources of energy.

Energies 2021, 14, 4916. https://doi.org/10.3390/en14164916 https://www.mdpi.com/journal/energies

Energies 2021, 14, 4916 2 of 54

Energy derived from biomass and biomass waste/residue is attracting a lot of attention.
The term biomass refers to all biological matter, i.e., plants, animals, microorganisms,
agricultural and forestry residue/waste, marine waste, and municipal and industrial
organic waste that is directly or indirectly derived from the process of photosynthesis [2,3].
Biomass is an abundant, cheap, renewable, and environmentally friendly source of energy.
Biomass and biomass waste can be used as a fuel, commonly called biofuel, which is
produced from organic matter. It is more difficult to handle, store, and transport biomass
than to do the same with conventional solid, liquid, and gaseous fossil fuels [4,5]. Biomass
is bulky and has low energy density, and a high moisture and low ash content [4,6].
Hence, over the years, numerous technologies and methods have been explored to convert
biomass into high-density, clean, and easy-to-handle solid, liquid, and gaseous fuels. The
first-generation biofuel sources, such as corn, edible oils, and other cereals, are also required
to fulfill dietary needs, while the second-generation biofuel sources, such as agricultural
and forest residues, wood chips, and pulp/paper remains are available in abundance
and can be converted into biofuel. The biofuel from second-generation resources can be
produced mainly through biochemical and thermochemical pathways. The thermochemical
routes comprise a vast range of technologies, such as combustion, pyrolysis, gasification,
and hydrothermal liquefaction (HTL). As biomass contains large amounts of inherent
moisture, the thermal treatment—especially combustion, pyrolysis, and gasification of
biomass without drying—is problematic and less efficient.
The hydrothermal (HT) process can handle resources with high moisture. HT pro-
cessing involves the thermochemical conversion of biomass in the presence of a hot and
pressurized solvent medium long enough to hydrolyze and degrade the lignocellulosic
matter into biofuel [3]. HT processes are broadly classified into three categories depending
on temperature and pressure conditions, as shown in Figure 1. The operation that occurs at
a temperature range of 180–250 ◦ C and pressures of 2–10 MPa is called HT carbonization,
and the major product obtained is char [7]. The operation that occurs at an intermediate
temperature range between 250 and 374 ◦ C and pressures of 2–25 MPa is HT liquefaction
(HTL) and is used to produce high energy-dense liquid fuels, such as bio-oil [8,9]. The
major product above critical condition of water 374 ◦ C, 22 MPa is gas, the operation in
this zone is called HT gasification [10]. In this review, we will limit our discussion to the
HTL process. There are few important reasons for limiting the discussion to HTL process.
First, the HTL process produces two high quality products hydrochar and bio-oil. The
property of hydrochar produced from HTL is very similar to the biochar produced from
HTC process, which makes it more advantageous to cover HTL process in this review over
HTC. Second, the operation condition for HT gasification is higher when compared to HTL,
which makes HT gasification less economic in comparison to HTL. Lastly, HTL is a very
broad topic, which involves the study of several parameters for its complete understanding.

Figure 1. Different hydrothermal processing routes, reaction condition, and products (HT–hydrothermal) [3,11–18].
Energies 2021, 14, 4916 3 of 54

This review examines the state-of-the-art HTL process. Section 1 introduces the
HTL process, lists the major feedstocks, discusses about the HTL reaction mechanism,
and details about the type (batch and continuous), and scale (laboratory, bench, and
pilot) of HTL operations, followed by extraction procedures and calculation methods.
Section 2 provides a detailed discussion about the effect of various process parameters,
primarily from the point of view of optimizing bio-oil yield. The role of various catalysts
and solvents in the HTL process and their effects on the product yield and quality are
discussed in Section 3. Section 4 summarizes various HTL products, their characteristics,
and applications. Sections 5 and 6 provide concluding remarks, address research gaps, and
suggest topics for future study.

1.1. Hydrothermal Liquefaction

HTL is also known as hydrothermal treatment or hydrothermal upgrading. As shown
in Figure 1, the optimum range of HTL operations is in the temperature range of 250–374 ◦ C
with a final pressure of 2–25 MPa. In general, water is used as a process medium. Using
water as a medium benefits the hydrolysis reaction that occurs in HTL. Removing moisture
can be a costly pre-treatment step in techniques like combustion, pyrolysis, and gasification.
However, as there is no need to pre-treat biomass to remove moisture, HTL is considered a
more economical alternative for bio-oil production. HTL has been used for a long time. A
recent review by Gollakota et al. [19] provides a detailed history of the evolution of HTL.

1.2. Major Lignocellulosic Biomass Feedstocks and HTL Mechanism

Agricultural and forest residue are two main sources of lignocellulosic biomass. The
name lignocellulosic mainly describes the key structural components—lignin, cellulose,
and hemicellulose—present in agricultural and forest biomass. The elemental compo-
sition mainly consists of carbon, hydrogen, and oxygen with traces of nitrogen, sulfur,
and mineral impurity. Some major feedstocks along with their structural and elemental
compositions are described in Table 1.
Cellulose is a homo-polysaccharide formed by the linearly coupled D-glucopyranoside
units connected by β-glycosidic linkages in a 1:4 fashion [20]. Increased packing density in
cellulose structure leads to the formation of crystalline structures, which are insoluble in
an aqueous medium under normal conditions and require rigorous treatment for hydrol-
ysis and degradation, whereas the non-crystalline structure is easily hydrolyzed [21,22].
Hemicellulose is mainly composed of D-glucose, D-xylose D-mannose, and D-galactose
along with some other glycosyls. It has a poor structural formation leading to a reduced
crystallinity, making it more susceptible to water [2]. Lignin is a three-dimensional struc-
ture made of ether bonds and C–C linkages. The three main monomeric units of lignin are
p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol [14].

Table 1. Chemical and elemental composition of major feedstock and bio-oil yield.

Feedstock Cellulose Hemicellulose Lignin Carbon Hydrogen Oxygen H/C O/C Bio-Oil Ref.
Agricultural Feedstock
Corn straw 30.81 25.52 16.76 44.57 5.53 33.70 1.49 0.57 7.9 [23]
Peanut straw 36.56 20.27 18.36 41.42 5.51 35.21 1.60 0.64 14.6 [23]
Rice straw 46.33 31.09 10.17 41.34 5.33 34.29 1.55 0.62 15 [23]
Soybean straw 42.39 22.05 18.93 45.99 6.07 39.00 1.58 0.64 15.8 [23]
Corn stover 45.00 30.00 16.00 43.57 5.84 49.98 1.61 0.86 27.15 [24,25]
Rice straw 42.87 25.15 31.97 38.55 5.50 55.34 1.71 1.08 27.6 [26]
Barley straw 46.00 23.00 15.00 44.66 6.34 47.97 1.70 0.81 34.9 [27]
Castor residue 38.42 22.40 20.20 43.59 5.56 46.16 1.53 0.79 15.8 [28]
Pre-treated sorghum bagasse 49.84 8.01 24.65 43.20 5.80 41.40 1.61 0.72 23.42 [29]
Energies 2021, 14, 4916 4 of 54

Table 1. Cont.

Feedstock Cellulose Hemicellulose Lignin Carbon Hydrogen Oxygen H/C O/C Bio-Oil Ref.
Forest Feedstock
Oakwood 38.10 23.00 32.00 50.20 7.00 42.80 1.67 0.64 23.17 [30,31]
Palm kernel shell 24.50 22.90 33.50 47.77 4.06 47.55 1.02 0.75 24 [32]
Empty fruit bunch 26.60 26.90 18.60 43.62 4.03 50.22 1.11 0.86 16 [32]
Palm mesocarp fiber 23.10 22.20 30.60 46.29 4.67 47.37 1.21 0.77 16 [32]
Poplar wood 52.16 18.92 22.97 47.04 5.60 43.20 1.43 0.69 28.49 [33]
Birch sawdust 45.30 24.20 22.90 48.50 6.30 45.20 1.56 0.70 22.3 [34]
Aspen wood 47.14 19.64 22.11 50.39 6.19 43.23 1.47 0.64 20.65 [35]
Datura stramonium L. stem 42.20 23.13 24.33 43.55 5.98 49.70 1.65 0.86 32 [36]
Poplar wood 44.95 34.05 25.85 46.72 6.18 46.96 1.59 0.75 17.5 [37]
Furniture sawdust 32.63 37.23 22.16 47.42 5.67 46.71 1.43 0.74 12.1 [38]
Cypress 46.30 27.60 28.80 48.90 6.00 44.80 1.47 0.69 27.5 [39]
Pine 39.54 20.61 30.15 49.52 6.49 43.89 1.57 0.66 24.2 [40]
Paulownia 42.35 25.22 23.44 45.50 6.30 48.20 1.66 0.79 27.01 [41]
Oil palm shell 39.70 21.80 32.50 50.01 7.66 29.02 1.84 0.44 18.5 [42]
Beech wood 45.05 31.50 22.25 44.68 6.08 49.24 1.63 0.83 22 [43]
Scotch pine 47.30 20.54 27.70 48.33 6.49 45.18 1.61 0.70 24.6 [44]

1.2.1. Cellulose Decomposition

In the hydrothermal process, cellulose reacts with water at an elevated temperature,
which breaks the hydrogen bond in the cellulose, weakening its crystallinity. Cellulose
is hydrolyzed into glucose, fructose, and other monomeric units, which is followed by
further degradation of these units in simpler hydrocarbons. The pathway of cellulosic
hydrolysis and C–O–C bond cleavage can be different according to the acid, the base, and
the neutral medium, as shown in Figure 2a [45]. For instance, acid hydrolysis takes place
by the reaction of the acidic proton and oxygen that bonds two glucose units and forms the
conjugated acid, which, on the cleavage of glycosidic bonds, forms two glucose units [46].
In basic medium, the breaking of the C–O–C bond occurs when the OH− attacks at the
anomeric carbon, whereas in the presence of water, the glycosidic unit and water split at
the same time and form two glucose units [47].
Hirano et al. [48] presented the plausible mechanism for cellulose hydrolysis and
inferred that the major monomeric units formed are glucose and fructose, which, on
condensation and isomerization, produce unstable intermediates, such as erythrose, gly-
colaldehyde, dihydroxyacetone, and its reversible isomer, glyceraldehyde. Erythrose on
hydrogenation produces erythritol. The intermediate erythritol and glyceraldehyde further
dehydrate to form 2,3-butanedione and pyruvaldehyde, respectively. Some major interme-
diate reaction that occurs during HTL of cellulose is shown in Figure 2b. In the presence
of catalysts that promote hydrogenation, these intermediates result in the formation of
stable C2 –C3 alcohols, such as 3-hydroxy-2-butanone, hydroxy acetone, 2,3-butanediol,
propylene glycol, and ethylene glycol.
Li et al. [49] found the final composition from cellulose HTL to be a mixture of
esters, aldehydes, ketones, and a small fraction of alcohol, and ether. Esters, being the
most abundant, were devised to be formed via an α-hydrogen donation to intermediates,
resulting in the formation of majorly 2-hydroxy-acetic acid ethyl ester, 2-hydroxy propanoic
acid ethyl ester, and 4-oxo-pentanoic acid ethyl ester. The aldehyde and ketones formed
because of a series of decomposition, dehydration, isomerization, and aldol reactions. Gao
et al. [50] investigated the effect of temperature on cellulose decomposition and found that
at 200 ◦ C, 50% of the products were 5-HMF (5-hydroxy methyl-2-furancarboxaldehyde),
10% were ketones (major: 4-hydroxy-4-methyl-2-pentanon), and 5% were acids, such as
acetic acid, levulinic acid, and n-hexadecanoic acid. At higher temperatures of 300–400 ◦ C,
products were more distributed in a class of acids, aldehydes, ketones, furans, esters,
phenols, phenyl, and nitrogenous compounds.
Energies 2021, 14, 4916 5 of 54

Figure 2. (a) Proposed routes of HTL of cellulose (adapted Sudong et al. [45]), copyright from Elsevier 2012, (b) major
intermediate reactions during HTL of cellulose.
Energies 2021, 14, 4916 6 of 54

In order to understand the degradation characteristics of empty fruit bunch, Miyata

et al. [51] studied the effect of model substrates (cellulose, xylan, glucose, xylose, dihydrox-
yacetone, pyruvaldehyde, and hydroxyacetone) in enhancing the yield of water-soluble
(WS) product. Later, through catalytic cracking the WS product was converted to bio-oil. It
was found that non-catalytic HTL of cellulose, xylan, glucose, and xylose yielded 58 wt%,
64 wt%, 53 wt%, and 64 wt% of WS, respectively. In case of Fe-assisted HTL, the production
of WS from cellulose increased to 93 wt%, glucose to 74 wt%, and xylan and xylose both to
80 wt%. It can be said that cellulose can significantly enhance the production of bio-oil in
the presence of metal catalysts.
The yield of bio-oil significantly depends on the biochemical composition of biomass.
The weight percentage of cellulose content and the ratio of wcellulose /whemicellulose in
biomass are two important factors affecting the yield. Figure 3a shows the plots of dif-
ferent studies involving agricultural feedstock with varied composition. These studies
showed that cellulose content plays a dominant role in deciding the yield of bio-oil in
the case of agricultural feedstock. The plotted analysis of results from previous stud-
ies on different forest-based feedstocks as shown in Figure 3b it was observed that the
wcellulose /whemicellulose ratio was dominant over the cellulose content in determining the
bio-oil yield for forest feedstock.

Figure 3. Effect of cellulose and cellulose/hemicellulose ratio on bio-oil yield for (a) agricultural feedstocks [23–28], (b) forest
feedstock [26,27,29,32,33,35,38,40,41].

1.2.2. Lignin Decomposition

The ether bond connecting three basic phenylpropane units in lignin has a low bond
dissociation energy and the macromolecular unit is hydrolyzed in the presence of sub- and
supercritical water, forming the basic units of p-coumaryl alcohol, coniferyl alcohol, and
sinapyl alcohol. The basic units undergo further dissociation by hydrolysis of the side
C–C bonds to form aromatics [52]. The primary components obtained during softwood
lignin decomposition are guaiacols, catechols, and alkylphenols. Guaiacols, catechols, and
alkylphenols are mostly formed via hydrolysis and the breaking of ether and C–C bonds. In
a high temperature HTL environment, catechols and alkylphenols are also formed through
the demethoxylation of guaiacols and the alkylation of hydroxylated benzene, respec-
tively [52,53]. The formation of cresols, ethyl phenols, and methyl benzenediols takes place
through the alkylation of respective phenols and benzenediols as shown in Figure 4 [54,55].
Nguyen et al. [56] performed a temperature study on the product composition of lignin
liquefaction and found that the fraction of guaiacols and phenolics dimers decreased sig-
nificantly when the temperature in the sub-critical zone increased at the same time that
the fraction of alkylphenols, anisoles, and catechols increased. In summary, cellulose and
hemicellulose mainly contribute to the formation of acids, esters, fatty acid alkyl esters,
Energies 2021, 14, 4916 7 of 54

ketones, aldehydes, furans, alcohols, and ether, whereas lignin mostly dissociates to form
aromatic compounds.

Figure 4. Proposed pathway for hydrothermal lignin decomposition [55], copyright Elsevier 2013.

1.3. Hydrothermal Liquefaction Process

1.3.1. Batch Process
Most HTL experiments have been studied in a batch reactor at a laboratory scale,
though there has been a significant improvement in pilot scale studies in a continuous
system over the last 10 years. In general, the batch reactor studies have been carried out in
a cylindrical autoclave reactor made of either stainless steel, Hastelloy C-22, or Inconel-625
with a typical size of 100–1000 mL. Some studies used a tubular reactor (25 mL) made of
stainless steel, whereas a self-assembled Swagelok port connector and caps also serve as
a batch reactor [57]. The typical assembly of a batch reactor consists of a stirrer, inlet and
outlet tubes, valves for gas pressurization and depressurization, a heating and cooling
system, temperature detector, pressure gauge, and controller. The heating system can be
either an external electric furnace, coil heating, or sand bath heating. The cooling system
can be an electric fan or chilled water with tubular coil. Other than that, the reactor is
connected to a gas cylinder to provide an initial pressure (inert gas) to prevent a phase
change during the process. It also contains a temperature detector. Once the reactor is
loaded with feedstock and solvent, it is purged with an inert gas and pressurized with
either an inert gas or a process gas. One common challenge faced with conventional batch
reactor is the long time it takes to reach the final process temperature and similarly long
time required for its cooling, which notably increases the overall time spend by products
at a relatively high subcritical temperature regime. The problem with the long heating
time is the side reactions associated with it, which decreases the total oil yield. Brand
et al. [58] discussed the effect of heating rate on bio-oil yield and found that a combination
of fast heating rate, high temperature, and immediate quenching can highly improve the
yield of bio-oil. Another problem associated with the batch reactor is the improper mixing
of biomass-water slurry, which leads to formation of dead zones at bottom corners. The
Energies 2021, 14, 4916 8 of 54

biomass accumulates in the dead zones, giving rise to incomplete conversion and formation
of char.

1.3.2. Continuous Process

In the batch process, the reactor takes a long time to reach the final temperature; the
long heating time to reach subcritical temperature promotes enhanced degradation. How-
ever, the process with the final temperature as the critical condition of water, the heating
time is significantly longer; this long heating time promotes a side reaction, resulting in
intermediate formation, repolymerization, and cracking. One objective of moving from
a batch to a continuous system is to achieve a fast-heating rate at high temperature. The
heating time in the continuous system is adequate to support easy hydrolysis and decom-
position of biomass while eliminating side reactions, which happens during a long heating
time. Converting higher amounts of biomass in a small processing unit requires a high-
pressure feeding system for concentrated biomass slurries, which is another technological
challenge in process development [10].
Limited research has been conducted in the field of a large-scale continuous HTL
process for bio-oil production using lignocellulosic biomass. Toor et al. [59] studied the
catalytic liquid conversion of wet distillers’ grain with solubles (WDGS) in a 30 dm3 h−1
continuous pilot plant at a subcritical temperature of 350 ◦ C and a pressure of 25 MPa with
the feed flow maintained at 11 dm3 h−1 . A high-pressure feed pump and recirculation
pump were used to maintain a high flow rate. In order to heat the feed mixture quickly,
the recirculating pump was designed to supply nine parts of pre-heated feed to mix with
one part of new feed, which then reached the operative temperature with a small addition
of heat through a trim heater. Mørup et al. [60] developed a batch autoclave assembly,
which he called a stop-flow reactor system. It had a capacity of 170 mL with inlets and
outlets allowing injection of feed and ejection of the product one at a time at elevated
temperatures. The system also had a high-pressure to maintain the temporary flow mode
in reactor. The reactor supported fast heating and performed multiple identical runs in a
sequence without needing to be cooled. High-pressure pneumatic pumps were used to
inject and eject materials.
Anastasakis et al. [61] used an Aarhus University pilot-scale HTL reactor for lique-
faction of miscanthus, spirulina, and sewage sludge. The HTL system was a 140 m long
tubular set-up of a constant cross section (14.2 mm) with a total system volume of 20 L.
The feeding system consisted of a progressive cavity pump for continuous recirculation
slurry in a hopper. To support an efficient flow rate, a positive displacement pump with
a flowrate capacity of 600 L h−1 and delivery pressure capacity of 476 bar was used to
deliver feed at a flow rate of 60 L h−1 at a pressure of approximately 220 bar. A double-
pipe counter-current heat exchanger was used for initial heating of slurry with a K-type
thermocouple. After the heat exchangers, the slurry passed through the trim heater, which
consisted of 32 independent electric heaters (heating capacity 1 kW each) to increase the
temperature of the slurry to match the reaction temperature. The reactor assembly was
a 10-pipe system with five convolutions. It was surrounded by heating tapes with 1 kW
of power. To prevent heat loss, the hot zones were heavily insulated with stainless steel
casing. To increase the turbulence in the system for better mixing and heat exchange, a
novel two-piston (0.5 L) hydraulic oscillation system was used, and a similar hydraulic
system was used at product take-off. The product collection zone consisted of a hydro
cyclone to separate the liquid and gaseous stream, and a separating funnel to separate the
different phase liquid products.
There are a few more big projects focused on scaling HTL operations to understand
large-scale process parameters and operational technicality and economics. Elliott et al. [10]
published a detailed review of continuous systems and explored HTL pathways at inter-
mediate conditions to produce bio-crude, understand energy balance, and cost analysis.
Castello et al. [62] examined state-of-the-art continuous HTL process with data interpre-
tation from existing literature. Tran et al. [63] proposed a conceptual model for a tubular
Energies 2021, 14, 4916 9 of 54

plug flow system, focusing on the key objective of making an efficient HTL continuous
system. The major objectives were achieving prompt, strong, and uniform mixing for
proper heating and conversion, short residence time to avoid char formation, rapid heating
of slurry in a reactor to prevent side reactions, and speedy downstream flow of products
out of the reactor to avoid accumulation.
Tran et al. [63] pointed out some of the main problems faced during a continuous
plug-flow operation. The formation of char from incomplete conversion of biomass and
that of coke from decomposition of bio-oil leads to clogging of the reactor over several
hours of operation. Use of a catalyst can limit the formation of side products, though
the cost of catalysts and the challenges to recover catalysts increases the total cost of the
process. The limited availability of data and tests conducted on a high-pressure feeding
system of high concentration slurries makes it difficult to estimate the economic cost of
large-scale operation. Thus, a high-pressure feeding system for biomass slurries remains a
technological challenge in development of HTL process [10].

1.3.3. Extraction Methods and Product Calculations

The HTL experiment consists of two main steps: the reaction process and the extractive
product separation. The first part of the experiment includes loading feedstocks in the
reactor, followed by the reactor heated to its final temperature and then being cooled until
it comes back to room temperature. The next step includes separating various product
fractions: bio-oil, aqueous phase, char, and gas. There are several methods of product
separation with some differences in the liquid phase separation step. Once the reactor
reaches room temperature, it is depressurized, all the gaseous products are collected in a
Tedlar bag, and the composition is analyzed with gas chromatography (GC) equipped with
either a thermal conductivity detector (TCD) or flame ionization detector (FID). The reactor
is opened, and the product mixture is filtered using filtration and filter paper to separate the
solid fraction from the aqueous medium. The solid residue stuck to the reactor’s bottom,
sides, and stirrer is recovered using an extractive solvent, such as acetone [64–66]. The solid
fraction is washed a few times with acetone to recover all of the organic phase from its pores.
It is mixed with acetone recovered from the reactor. The acetone-phase mixture is treated
in a rotary evaporator to remove the acetone or else the acetone phase is centrifuged at a
high speed to separate out the acetone. The collected product is dark brown. This highly
viscous phase is commonly referred to as heavy oil or bio-crude. A solid residue, it is dried
at room temperature or in an oven before undergoing elemental analysis to understand its
composition, Fourier transformation infrared spectroscopy (FTIR), to study the presence of
functional groups on its surface, and a morphology study. The aqueous medium consists
of a water-soluble organic phase and inorganic phase based on the type and composition of
feedstock and the catalyst used. Instead of acetone, many other extractive solvents, such as
tetrahydrofuran (THF) [67], toluene [32], dichloromethane (DCM), methyl tert-butyl ether
(MTBE) [68], ethyl acetate (EAC), isopropyl alcohol (IPA), and hexane [69] have been tested.
In general, the water is evaporated from the aqueous medium and the product is
referred to as aqueous phase oil. Karagoz et al. [70] focused on the detailed extraction of
different oil phases from an aqueous medium using a liquid–liquid extraction method. For
this, aqueous organics were first extracted using diethyl ether (DEE) and the remaining
water phase was again extracted with EAC. Both solvents were evaporated to obtain
different oil fractions along with oil obtained from the acetone phase during the solid wash.
In a similar extractive procedure with different extractive solvents, Wang et al. [71]
used benzene, hexane, and THF to obtain a bio-oil fraction, asphaltene fraction, and pre
asphaltene fraction.
The various oil fractions are characterized for both physical properties and chemical
compositions. The most common tests performed to understand the physical properties of
oil are a viscosity measurement, total acid number analysis, water content analysis, and
iodine value analysis. Similarly, the chemical composition is obtained from CHNS and gas
chromatography and mass spectroscopy (GCMS) analysis.
Energies 2021, 14, 4916 10 of 54

The product yield is calculated based on the way different products are collected.
Some of the calculations can be generalized as shown below:

Weight o f f eedstock − Weight o f solid residue

Total conversion (wt.%) = × 100 (1)
Weight o f f eedstock

Weight o f solid residue

Weight o f solid residue (wt.%) = × 100 (2)
Weight o f f eedstock
Weight o f heavy oil
Weight o f heavy oil (wt.%) = × 100 (3)
Weight o f f eedstock
Weight o f oil phase
Weight o f other oil phase (wt.%) = × 100 (4)
Weight o f f eedstock
In cases where the weight of the gaseous product is measured, its percentage is simply
calculated as [23,72]:

Weight o f gaseous product

Weight o f gas (wt.%) = × 100 (5)
Weight o f f eedstock

In cases where it is not practical to record the weight of the gas phase, its weight
fraction is calculated using the difference between reactor loading and recovered mix-
ture weight:

Weight loaded ( f eedstock + solvent) − Weight recovered f rom reactor

Weight o f gas (wt.%) = × 100 (6)
Weight recovered f rom reactor

2. Effect of Process Parameters

The effect of various process parameters such as temperature, pressure, retention time,
heating rate, and biomass-to-solvent ratio is discussed in this section. Table 2. briefly sum-
marizes the outcomes on some major studies focusing on the effect of process parameters.

Table 2. Some major studies on the effects of temperature, pressure, retention time, feed ratio, and heating rate.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

The maximum bio-oil yield (49 wt%) was obtained at
HTT of microalgae: evaluation of the 375 ◦ C, 5 min. Up to 75% of the calorific value of algal
process as conversion method in an algae biomass can be retrieved in oil phase.
biorefinery concept. With high oil yield, its pronounced increase in nitrogen
1 2011 [73]
To understand the effect of wide range of content was observed (6 wt%).
condition (175–450 ◦ C, up to 60 min) to The dissolved inorganic N and P content in the aqueous
obtain the optimum range. phase points at recycling of the nutrients for next
generation algal growth.
Bio-crude obtained in the study has properties in range
Effect of operating conditions of with the petroleum crude and could be further refined to
2 2011 thermochemical liquefaction on bio-crude obtain transportation fuel. [74]
production from Spirulina platensis. Carbon conversion efficiency of 98.3% was obtained at
350 ◦ C, 60 min, and 20% solid concentration.
Bio-crude production from secondary
pulp/paper mill sludge and waste Addition of catalyst at 300 ◦ C was found to increase the
newspaper via co-liquefaction in yield of heavy oil.
3 2011 hot-compressed water. Synergistic effect was observed on the yield of bio-oil [75]
Investigate the effect of temperature and when secondary pulp/paper mill sludge and newspaper
selected catalyst (HCOOH, KOH, and FeS) waste was used.
on product yield.
Energies 2021, 14, 4916 11 of 54

Table 2. Cont.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

It was observed that at a temperature of 200 ◦ C,longer
retention time of 30 min gave higher yield, whereas at
To understand the effects of different
250 ◦ C and 300 ◦ C, shorter retention time of 0 min was
4 2012 reaction conditions on HTT of cornelian [76]
more effective.
cherry stones and bio-oil composition.
The major compound observed in heavy bio-oil was
linoleic acid at both 250 and 300 ◦ C.
Longer retention time did not facilitate increased
Characterization of products from
production of oil.
HTL of cellulose.
5 2012 The residual char had core-shell structure, the core [50]
Effect of temperature and residence time
contained ketone and ether groups and the shell
on HTL process.
contained carboxylic and carbonyl groups.
HTL of Litsea cubeba seed to In this study, Na2 CO3 suppressed the polymerization
produce bio-oils. pathways and, hence, negatively impacted the yield of
6 2013 Effect of temperature, residence time, bio-oil, which is contradictory to other studies. [57]
reactor loading, and catalyst concentration The bio-oil yield increased with increase in reactor
was studied to maximize production. loading up to a certain extent.
In case of subcritical water, no significant effect of
heating rate was observed for lower temperature of
Effect of heating rate on biomass
250–280 ◦ C, whereas significant change in conversion
liquefaction: Differences between
7 2014 and bio-crude was observed for temperature [58]
subcritical water and
above 315 ◦ C.
supercritical ethanol.
Only a marginal effect of supercritical ethanol as solvent
was observed on HTL conversion and bio-crude yield.
Alkaline pretreatment disrupts surface barriers and
increases surface availability of biomass.
Alkaline pretreatment and HTL of cypress
Alkaline pretreatment helps to suppress the
8 2014 for high yield bio-oil production. [39]
re-polymerization reactions during HTL.
Understand the reaction mechanism.
It markedly enhanced the bio-oil yield at
optimum temperature.
The effect of temperature on the catalytic As the temperature increased the yield of water-soluble
conversion of Kraft lignin using near organics increased (5–11 wt%), bio-oil decreased
critical water. (87–69 wt%) and that of char increased (16–22 wt%).
The catalytic conversion was studied The yield of catechols, alkylphenols, and anisoles
9 2014 using ZrO2 /K2 CO3 catalyst and phenol increased with increase in temperature whereas the mass [56]
as co-solvent and char suppressing agent. fraction of guaiacols and phenol dimers decreased.
The reaction temperature studied were Total mass fraction of phenol-free compounds increased
290–370 ◦ C in a continuous flow reactor with increase in temperature in both water-soluble
with feed flow of 1 kg h−1 . fraction and lignin bio-oil.
Bio-oil production from oil palm biomass The optimum condition for HTL of all oil palm biomass
(empty fruit bunch, palm mesocarp fiber, was 390 ◦ C and 25 MPa with bio-oil yield of palm kernel
10 2014 [32]
and palm kernel shell) via subcritical and shell (38.5 wt%) > empty fruit bunch (37.4 wt%) > palm
supercritical HTL. mesocarp fiber (34.3 wt%).
HTL of rice straw: effect of HTL in N2 environment produced highest bio-oil
reaction environment. (17 wt%), whereas it was lowest in case of O2 .
11 2015 [77]
Effect of N2 , O2 , and CO2 on In O2 atmosphere oxidation of some phenolic
product distribution. derivative occurred.
At 410 ◦ C, highest conversion of 90% with heavy oil yield
High conversion of miscanthus using sub- of 22 wt% and light oil yield of 12 wt% was obtained.
12 2015 [78]
and supercritical water above 400 ◦ C. The gaseous fraction increased significantly at a
temperature of 460 ◦ C.
Energies 2021, 14, 4916 12 of 54

Table 2. Cont.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Maximum bio-crude yield of 34.9 wt% was obtained at
300 ◦ C with pure water. On aqueous phase recirculation
at 300 ◦ C, the bio-crude yield increased to 38.4 wt% after
HTL of barley straw to bio-crude oil. three aqueous phase re-circulations.
Understanding the effect of reaction The aqueous phase was composed of alcohols, polyols,
13 2015 [27]
temperature and aqueous phase and -oic acids.
recirculation. Major compounds in bio-crude oil were phenolic,
carboxylic acids, aldehydes, and alcohols.
Recirculation facilitated higher carbon content in
solid char.
The highest yield of crude bio-oil was experimented to
be 47.3 wt% at 275 ◦ C, 10 min, 1/20 (biomass/water
HTL of spent coffee grounds in water
ratio) and initial pressure of 2 MPa.
medium for bio-oil production.
14 2016 Crude bio-oil molecular weight decreased from 200 ◦ C [79]
Effect of temperature, retention time,
(769 g mol−1 ) to 300 ◦ C (479 g mol−1 ). Similarly, crude
pressure, and biomass/water ratio.
bio-oil m. wt. decreased with increase in retention time
10 min (479 g mol−1 ) to 30 min (433 g mol−1 ).
The simulated distillation characteristics of bio-oil
Conversion of waste bamboo chopsticks
obtained in the study are close to diesel.
to bio-oil via HTL using K2 CO3 .
15 2016 K2 CO3 was an effective catalyst for HTL of feedstock [80]
Understanding the effect of temperature,
such as bamboo chopsticks, which have very high lignin
retention time, and catalyst on HTL.
content 25.5 wt%.
The bio-oil obtained in the study has high heating value,
Optimization of bio-oil production by
low ash content and the boiling point lies in range for
HTL of agro-industrial residues:
upgrading to useable fuels. However, the acidity and
blackcurrant pomace as an example.
16 2016 viscosity of oil suggest a need for further [81]
The objective is to study temperature,
upgradation of oil.
retention time, slurry concentration, and
The low influence of retention time suggest continuous
pH effect on bio-oil yield.
reactor of shorted residence can be adapted.
Most of the obtained compounds in products can be
classified in five categories: methoxybenzene, guaiacols,
catechols, alkylphenols (methyl, ethyl), and
HTL of lignin in a new batch reactor in
phenolic dimers.
near critical water: influence of phenol
With increased temperature, the fraction of phenol-free
and temperature.
17 2017 components increased in both water-soluble organics [53]
Demonstration of a new batch reactor
and bio-oil.
encompassing fast biomass heating,
With an increase in the phenol fraction as a co-solvent in
pressure control, and product quenching.
the feed, total solid residue formation decreased and the
phenol-free yield of lignin derived 1-ring aromatic
compound increased.
Bio-crude production via supercritical
Hydrothermal co-liquefaction of spent
mushroom compost and aspen A bio-crude yield of 48 wt% was obtained using spent
wood sawdust. mushroom compost at 400 ◦ C, 15 min in the presence of
The work focuses on supercritical K2 CO3 catalyst. It also produced 50 wt% solid fractions.
18 2017 [35]
catalyzed and non-catalyzed HTL at Co-liquefaction of spent mushroom compost along with
400 ◦ C, 15 min. aspen wood sawdust in a ratio of 1:3 helped to reduce
Study on co-liquefaction with aspen wood solid fraction to 24.5 wt%.
and acid leaching aimed at
solid reduction.
Energies 2021, 14, 4916 13 of 54

Table 2. Cont.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Co-liquefaction of spent coffee grounds
The optimum temperature was 250 ◦ C, with mixing
and lignocellulosic feedstocks.
biomass ratio of 1:1.
Exploring the co-liquefaction of spent
Spent coffee grounds and corn stalks were identified as
coffee grounds with paper filter, corn
19 2017 the best feedstock combination for co-liquefaction with a [82]
stalk, and white pine bark.
significant positive synergistic effect. It was also found
The main objective was to obtain possible
that the overall oil quality improved in terms of viscosity
synergistic effect of different feedstock to
and relative molecular mass.
obtain bio-crude economically.
Highest yield of heavy oil (29. 5 wt%) was observed at
HTL of lignocellulosic biomass feedstock
300 ◦ C, final pressure 2200 psi and 0 min retention time.
20 2020 to produce biofuels: parametric study and [24]
The highest HHV was 35.5 MJ kg−1 obtained for heavy
product characterization.
oil yielded at 375 ◦ C.
The highest oil yield for different plastic material was
Oil from plastic via HTL: production found to be 32 wt% for PP (425 ◦ C, 30 min), 16 wt% for
and characterization. PET (450 ◦ C, 30 min), 60 wt% for PC (425 ◦ C, 30 min),
Effect of resident time and temperature and 86 wt% for PS (350 ◦ C, 30 min).
21 2020 [83]
was studied for HTL of polypropylene Depolymerization of plastic was fastest in
(PP), polystyrene (PS), polycarbonate (PC), supercritical water regime.
and polyethylene terephthalate (PET). The HHV value of oil from PS and PP was
comparable to gasoline.
The yield of light bio-oil increased on increasing
Catalytic HTL of Lactuca scariola with a
temperatures, from 220 ◦ C to 280 ◦ C,
heterogeneous catalyst: the investigation
22 2020 and decreased afterwards. [84]
of temperature, reaction time, and
The yield of heavy bio-oil increased with temperature,
synergistic effect of catalysts.
whereas that of solid residue decreased.
HTL of olive oil residue.
Bio-oil and solid residue yield of 30.8 wt% and 31.8 wt%
The objective was to obtain optimum
23 2021 was observed at optimum condition 300 ◦ C and [85]
process parameters for HTL of olive oil
15 min, respectively.
residue.
The highest yield of bio-crude was found to be over
Fast hydrothermal co-liquefaction of corn
24 w% at 400 ◦ C, 16 min, and CS:CW ratio of 1:1.
stover (CS) and cow manure (CW) for
For a fixed temperature of 400 ◦ C, the yield of bio-crude
bio-crude and hydrochar production.
24 2021 was maximum at CS:CM ratio of 1:1. [8]
Several reaction parameters, such as
The percent of phenolic compound was found to increase
residence time, reaction temperature, and
with residence time and was approximately 42.92% for
feedstock mass ratio were studied.
30 min residence time at 400 ◦ C and mass ratio 1:1.

2.1. Temperature
During most of the chemical process, temperature plays the main role in determining
the reaction pathways and kinetics. Similarly, in the HTL process, temperature is a domi-
nant factor, which decides major outcomes such as the total conversion of biomass, total
yield of different products, and the physicochemical properties of the products. Table 3
includes articles focused on the effect of temperature on the HTL of biomass in a range of
180–400 ◦ C. The temperature helps to increase the hydrolysis rate for cellulose, hemicel-
lulose, and lignin. It also promotes the fragmentation and degradation of lignocellulosic
biomass. The main role of temperature is to overshoot the transition state/energy barrier
between raw biomass and intermediates and move the process forward by providing
enough potential energy for bond breaking. Thus, the initial rise in temperature promotes
the endothermic step in the HTL process by providing the required activation energy
for bond cessation. As the bonds break, many unstable entities—primarily free radicals
and fragmented compounds—are formed. As the temperature is increased further, the
excited radicals repolymerize by forming new bonds and releasing energy, making HTL
exothermic in nature [86].
Energies 2021, 14, 4916 14 of 54

HTL process can have different optimal temperature points with respect to the total
conversion, bio-crude yield, and solid char yield, as well as in the context of producing
a higher fraction of a chemical composition in bio-crude. However, the present focus of
the HTL process is to produce bio-crude, and in this review, we will focus on an optimal
temperature for bio-crude yield. The optimal temperature in HTL depends on various
parameters. The most important is the type and composition of biomass used in HTL. The
type of solvents and catalysts, and the residence time, pressure, feed ratio, and heating rate
also affect the preferred temperature.
Many research groups have focused on the liquefaction study of the model compound
present in the lignocellulosic biomass. Minowa et al. [87] studied the decomposition of
microcrystalline cellulose decomposition in the presence of hot compressed water. It was
observed that on increasing the temperature from 200 ◦ C to 240 ◦ C all the products obtained
through hydrolysis, such as glucose and oligomers, were water soluble in nature. Non-
glucose products started forming only above 240 ◦ C. Simultaneously, primary products,
such as char, oil, and gas also formed. There was a rapid increase in the decomposition of
cellulose between 240 and 270 ◦ C, with a complete disassociation of cellulose and maximum
yield of glucose observed at 260 ◦ C. When the temperature was increased further, the yield
of the oil fraction increased and reached a maximum at 300 ◦ C. When the temperature
exceeded 300 ◦ C, the oil yield started to decrease, and the yield of char and gases started
to increase.

Table 3. Effect of temperature on HTL process and products.

Process Product HHV * C* H* O*

Feedstock Condition Yield (wt%) (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.

T *: 250–400 ◦C
Wood HO *: 17.4–35.5 63.8–77.9 1.4–9.4 14–34.7 -
Pi *: 2 MPa 15–28.4 [88]
(konara) Rt *: 30 min
Cunninghamia T: 280–360 ◦ C HO: 27.1–30.2 69.6–75.1 5.6–5.9 19.2–24.8 -
Rt : 10 min 19.3–23.8 [89]
lanceolata
Acetic acid (27%),
ketones (20%), aldehydes
High diversity LP *:
300–450 ◦ C 64–74 - (4%), benzenediols (17%), [90]
biomass phenolics (26%), phenyl
derivatives (7%)
Wood (Picea HO: 28.3–31.9 75.4 6.1 18.8 -
orientalis) 13.8–25.8
Wood 277–377 ◦ C HO:
(Quercus 27.9–31.6 75.2 6.1 18.9 - [91]
Rt : 25 min 15.9–27.1
robur)
Wood (Fagus HO:
16.8–28.4 27.6–31.3 75.1 6.0 19.1 -
orientalis)
280–360 ◦C
Wood HO:
Rt : 10 min 18.6–27 26.2 66.8 5.9 27.3 - [41]
(Paulownia) 60 g/360 mL
200–380 ◦ C
Spirulina Rt : 60 min BC *:
18–39.9 25.2–39.9 55.5–82.1 8.6–9.8 0.6–28.9 - [74]
platensis 20% solid
concentration
Acetic acid (1.3–5%),
LO *: phenolics (10.8–39%),
~3–6 20.8–22.5 58–60 5.3–5.8 34–36
furfurals (11–59%),
Cornelian 200–300 ◦ C vanillin (~3%) [76]
cherry stones Rt : 0 min
Furfurals (0.6–3.9%),
HO: 25.5–25.6 59.2–61.3 7.2–7.9 30.9–32.3 phenolics (~5%), -oic
~10–22
acids (45–61%)
Acids (14%), aldehydes
Microcrystalline 200–400 ◦ C HO: 25.01 69.9 4.2 25.9 (10%), furans (4%), esters
Rt : 30 min 5–14.75 (28%), phenolics (7%), [50]
cellulose
ketones (10%)
Phenolics (80.7%), other
Palm kernel 330–360 ◦ C BO *: - - - - aromatics (6.4%), ketones
shell P: 25 MPa 22.8–38.5 (6.7%), alcohols (3%), [32]
esters (3.3%)
Energies 2021, 14, 4916 15 of 54

Table 3. Cont.

Process Product HHV * C* H* O*

Feedstock Condition Yield (wt%) (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.

Empty fruit 330–360 ◦ C BO: Phenolics (72.8%), other

15.7–37.4 - - - - aromatics (10.7%),
bunch P: 25 MPa
ketones (16.5%)
Phenyl der (21%),
Swine T: 150–400 ◦ C BO:
Rt : 60 min 32.3 75 13.7 8.4 ketones (8.5%), furfurals [92]
carcasses 40.1–58.2 (5%), aldehydes (3.7%),
pH: 11
fatty acids (13)
Phenolics (5%), FAAE *
T: 280–400 ◦ C BC: 26.8–35.5 - - - (20%), ketones (3-4%),
Barley straw Catalyzed 19.9–34.9 cresol (2%), catechol (3%), [27]
alcohols

T: 200–300 ◦ C Hexadecanoic acid (48%),

Spent coffee BC: octadecanoic acid (15%),
Pi : 2 MPa, 31 71.2 7.1 18.7 [79]
grounds 16.6–35.3 octadecadienoic acid
Rt : 10 min
(35%)
Waste bamboo T: 290–380 ◦ C BO: 29.7–31 66.4–74.2 6.7–7.4 18.4–25.1 -
chopstick Catalyzed 7.1–21.2 [80]

Blackcurrant T: 290–335 ◦ C BO: Ketones (6%), FAAE (3%),

25.5–30 35.9 73.3 9.6 13.6 FA * (30%), FAM (10%), [81]
pomace Rt : 60 min
phenolics (9%)
Ketones (0.1–2.7%),
◦C phenol (1.1–6%), acids
T: 240–330 BO: 29.9–31.1 - - -
Coconut shell Rt : 30 min 7–13.9 (0.3–1.7%), furfurals [93]
(4–6%), polyols and
alcohols (0.4–6.3%)
Spent coffee
T: 225–325 ◦ C BC: 33.3 - - -
Long chain
ground + corn Rt : 10 min 10.2–21.6 [82]
carboxylic acids
stalk
Fatty acids, carboxylic
LO: acids, furan, aldehydes,
4.9–11.7 22.2–24.9 58.6–61.1 5.9–6.9 31.4–34.4
esters, phenols, ketones,
T: 200–300 ◦ C [26]
Rice straw Rt : 120 min alcohols, alkenes, alkanes
Carboxylic acids, ketones,
HO: 22.4–31.9 58.6–72.7 6.5–7.5 18.8–34.8
8.8–15.9 alkanes, alcohols, amines,
phenols
Ketones (2.1–9.6%), linear
saturated and
unsaturated HC (1–12%),
T: 250–375 ◦ C, phenyl compounds
Corn stover HO: 27.5–35.1 64.9–76.3 7.2–8.2 13.6–26.5 (3–7%), phenolic
Rt : 15 min, 14.3–27.2 [14,24]
Pi : 4 MPa derivatives (56–82%),
aldehydes, fatty acids,
and fatty acid
alkyl esters.
Ketones (17.81%),
Olive oil T: 250–330 ◦ C, BO: 25.6–31.8 63.8–70.9 6.6–7.9 19.9–28.5
phenols (43.56%), acids
residue Rt : 15 min 14.79–30.75 [85]
(0.69%), and esters
(10.47%)
* HO: heavy oil, BO: bio-oil, BC: bio-crude, LO: light oil, LP: liquid products, HHV; higher heating value, C: carbon, H: hydrogen, O:
oxygen; Pi : initial pressure, Pf : final pressure, T: temperature, Rt : retention time, FAAE: fatty acid alkyl ester, FA: fatty acids.

Arturi et al. [53] studied the liquefaction of lignin near critical water, at a temperature
range of 280–350 ◦ C in the presence of K2 CO3 as a catalyst, and a 3.2–3.6 wt% of phenol.
The results indicated a significant increase in bio-crude yield from 50.6 wt% to 77 wt%
when the temperature increased from 280 ◦ C to 300 ◦ C, followed by a steep decrease to
50.4 wt% when the temperature increased to 320 ◦ C. Similar trends of lignin decomposition
were also observed by Nguyen et al. [56]. The yield of oil was around 85–88 wt% at a lower
temperature of 290–310 ◦ C, which decreased to 69 wt% when the temperature was increased
to 370 ◦ C, whereas the fraction of char and water-soluble hydrocarbon increased with an
increase in temperature. Both Arturi et al. [53] and Nguyen et al. [56] observed that the total
phenol-free mass fraction increased with an increase in temperature. The mass fraction
of catechol and alkyl phenols (methyl, ethyl) also increased with a temperature increase.
Energies 2021, 14, 4916 16 of 54

However, the mass fraction of guaiacols, phenolic dimers, vanillin, and acetovanillone
decreased with an increase in temperature.
Mathanker et al. [24] published a parametric study to understand how the process
parameters, such as temperature (250–375 ◦ C), pressure (Pi : 2–4 MPa), and retention time
(0–60 min) affect the liquefaction of corn stover. It was observed that for the fixed initial
pressure of 4 MPa and retention time of 15 min, a yield of heavy oil reached a maximum
limit with an increase in temperature from 250 ◦ C (22.2 wt%) to 300 ◦ C (27.2 wt%), where
the yield of solid char was minimum. This was followed by a steep decrease in the oil yield
as the temperature rose to the super critical point of water 375 ◦ C (14.3 wt%). However,
it was observed that, though the yield of solid char was minimum at 300 ◦ C (21.4 wt%),
it increased with a further increase in temperature to 350 ◦ C (26.8 wt%), followed by a
decrease in the second half when the temperature increased to 375 ◦ C (22.4 wt%).
Zhu et al. [27] showed the HTL of barley straw in a temperature range of 280–400 ◦ C
with K2 CO3 as a catalyst. Initially, in a low temperature range of 280–320 ◦ C, there was no
significant change in the yield of products, mostly due to the continuous hydrolysis and
dehydration reaction, giving rise to the formation of intermediates. The maximum yield of
bio-oil occurred at 300 ◦ C (34.9 wt%), which decreased with an increase in temperature to
400 ◦ C (19.9 wt%). The study also indicated a decrease in the oil yield and an increase in the
solid char yield as the temperature increased from 320–400 ◦ C. Sun et al. [41] performed the
liquefaction of paulownia in hot compressed water in a temperature range of 280–360 ◦ C,
and obtained a similar trend of an increase in the heavy oil yield mass fraction from 280 to
300 ◦ C, followed by a continuous decrease to 360 ◦ C. Khampuang et al. [94] examined the
effect of temperature on the liquefaction of corncobs in supercritical ethanol for 60 min and
under an initial H2 pressure of 4 MPa and reported that the oil yield gradually increased
from 300 ◦ C (33.9 wt%) to 340 ◦ C (38.6 wt%), followed by a steep decrease at 360 ◦ C
(27.3 wt%). In the co-liquefaction study carried out by Yang et al. [82] on spent coffee
grounds with lignocellulosic feedstocks (paper filter, corn stalk, and white pine bark), the
optimum temperature for maximum bio-crude yield was found to be 250 ◦ C, whereas the
liquefaction of the spent coffee grounds alone in Yang et al. [79] showed the optimum
temperature to be 275 ◦ C.
Most of the studies that used agricultural crop residue, forest biomass residue, marine
biomass waste, and municipal solid waste as feedstock observed that, with an increase in
temperature, the bio-oil yield increased to a maximum, as shown in Figure 5; any further
increase in temperature resulted in a decrement in the mass fraction of bio-oil. It can be
said that the intermediate temperature range of 275–350 ◦ C supports a higher oil yield. At
a lower temperature range, <275 ◦ C, the biomass is not completely degraded, leading to a
higher unconverted solid residue. Moreover, the reactions are predominantly endother-
mic, supporting the formation of water-soluble organics and unstable entities. Even a
higher temperature (i.e., >350 ◦ C) does not favor bio-oil production as with an increase in
temperature the yield of solid and gas fraction increases. One possible reason could be
the promotion of the Boudouard reaction and hydrocracking at higher temperatures. The
Boudouard reaction between char and carbon dioxide, which produces carbon monoxide,
is endothermic in nature and is thus suppressed at a lower temperature, where much of the
supplied energy is used in the decomposition of biomass. However, at temperatures near
374 ◦ C, much of the repolymerization reaction and the resulting bond formation release
essential energy required to promote a side reaction supporting gas formation [3]. Secondly,
the formation of char that results from a repolymerization/condensation reaction due to the
availability of free radicals in the process leads to a decrease in the oil yield [27,86]. Hence,
it is the competition among the initial hydrolysis process, secondary repolymerization, and
cracking reaction, which decides the optimum temperature for the oil yield from a biomass.
Energies 2021, 14, 4916 17 of 54

Figure 5. Effect of final temperature on the yield of heavy oil for various feedstocks.

2.2. Pressure
Reactor pressure is another important parameter that can simultaneously promote
and hinder various reactions during the HTL process. In general, N2 , He, or Ar is used
as an inert media [88,95,96], as summarized in Table 4. Hydrothermal liquefaction occurs
at a temperature above the boiling point of water. Most of the solvents used in the study,
such as water, ethanol, methanol, DCM, acetone, phenol, and ethylene glycol, have a
boiling point below 100 ◦ C in atmospheric pressure conditions. During high temperature
operations, the inclination of these solvents is to split into two phases by exploiting the
system’s energy. An initial pressure maintained in the system helps to lessen the phase
transition of the solvent into vapor during subcritical and supercritical operations, thus
reducing the additional energy required to support a two-phase system [14,79].

Table 4. Effect of pressure on HTL process.

Process Product HHV * C* H* O*

Feedstock Condition Yield (wt%) (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties/Comments Ref.

Pi *: The yield was remarkably dependent on

Wood 0.5–10 MPa HO *: 31.6–35.5 73.6–76.9 7–8.1 13.9–19.4
(konara) T *: 350 ◦ C 5.9–20.1 pressure and maxed at initial pressure [88]
Rt *: 30 min of 4.0 MPa.
Pi : 0–10 MPa
T: 200 ◦ C HO: 3–5.8 - - - - There was a sharp increase in oil yield
Birch Rt : 30 min on increasing pressure from 0 to 2 MPa [97]
powder followed by a decrease in yield on
Pi : 0–10 MPa
T: 300 ◦ C, HO: 9.2–12.7 - - - - further increasing pressure until 9 MPa.
Rt : 30 min
Pi: 0.4–7.5 H/C: 1.43–1.47, O/C: 0.28–0.34
Red pine MPaT: The initial pressure head had negligible
370 ◦ C, Rt : BC *: 52–56 - - - - [98]
sawdust effect on conversion, bio-crude, and
30 min solid yield.
P: 25–35 MPa BO *:
T: 390 ◦ C 29.4–38.5 Phenolics (89.4%), other aromatics
(5.3%), ketones (5.3%).
Palm The decreased bio-oil yield at higher
mesocarp P: 25–35 MPa BO: 23.4–27.5 - - - - [32]
T: 360 ◦ C pressure in supercritical condition was
fiber
P: 25–35 MPa attributed to be the result of gasification
T: 330 ◦ C BO: 22.8–25.6 due to increased free radical reaction.

Poplar Bio-oil yield increased while solid

P: 0–4 MPa BO: 16–18 26.8 66.3 6.4 27.1 residue decreased with the increase [37]
wood in pressure.
Pi : 2–4 MPa HO: 29.6–30.3 68.3–69.4 7.4–7.5 21.5–22.7
T: 300 ◦ C 21.8–27.2 Effect of pressure was obvious in
Corn [24]
stover sub-critical temperature and negligible
Pi : 2–4 MPa HO: 14.3 35.1 76.3 8.2 13.6 near supercritical condition.
T: 375 ◦ C (No change)
* HO: heavy oil, BO: bio-oil, BC: bio-crude, HHV; higher heating value, C: carbon, H: hydrogen, O: oxygen, Pi : initial pressure, Pf : final
pressure, T: temperature, Rt : retention time.
Energies 2021, 14, 4916 18 of 54

In a subcritical region, an increase in the operating pressure increases the local density
of the solvent. An increase of pressure at 330 ◦ C from 25 to 35 MPa increases water density
by 22 kg m−3 and at 360 ◦ C by 44 kg m−3 [32]. The increase in local solvent density
allows more contact and better penetration and interaction of hydrolysis ions with the
crystallized zone of cellulose and the surface of cellulose, hemicellulose, and lignin. Once
the supercritical condition is achieved, the pressure has a negligible impact on the yield
of bio-oil [24,98]. The increase of pressure in the supercritical region increases the local
solvent density, causing a cage effect, which prevents C–C bond cleavage and thus reducing
the fragmentation of lignocellulosic material [86]. However, Chan et al. [28] performed
liquefaction of three forms of oil palm biomass (empty fruit bunch, palm mesocarp fiber,
and palm kernel shell) in a supercritical zone (390 ◦ C) and observed a decrease in the bio-oil
yield by 6–9 wt% when the operating pressure was increased from 25 to 30 MPa. In the
supercritical region, the effect of the pressure on the kinetics of the hydrolysis reaction is
relatively small. Even a pressure of 30–40 MPa may not be adequate to affect the hydrolysis
rate [99]. However, the selectivity of the cellobiose hydrolysis reaction increases. For
example, when the pressure is increased above the critical point, the isomerization rate of
glucose to fructose decreases and the retro-aldol condensation of glucose increases, whereas
with a decrease in pressure, the formation of 5-HMF and hydrolysis of oligosaccharides
increases [100].
In early studies, Ogi et al. [88] observed that on increasing initial pressure from 0.5 to
4 MPa, the bio-oil yield increased from 6 to 20 wt% and had a negligible effect on a further
increase in pressure up to 10 MPa at 350 ◦ C. Mathanker et al. [24] observed that pressure
had no effect on oil yield in the supercritical region (374 ◦ C), whereas at a 300 ◦ C increase
in initial pressure from 2 to 4 MPa, there was an increase in the bio-oil yield from 21 wt%
to 27 wt%. Similarly, Brand et al. [98], Yang et al. [79], and Tekin et al. [37] observed that
an initial pressure of inert N2 had little effect on the yield of bio-oil. They also found that
a starting pressure of 4–5 MPa helps to improve the yield of bio-oil as shown in Figure 6.
In the case of gaseous products, the role of pressure becomes significant after the critical
point of water; an increase in pressure above the critical point favors the formation of C2 ,
C3 , and C4 , and decreases yield of H2 and CO2 [101].

Figure 6. Effect of initial pressure in reactor on the yield of bio-oil (inert environment).

In order to understand the effect of various reaction environments, other gaseous

systems, such as H2 [96,97,102], CO2 [77], O2 [77], and CO [95], are also used. Yin et al. [95]
performed HTL of cattle manure in the presence of CO and N2 at 310 ◦ C and observed that
CO was the most effective process gas. Furthermore, an increase in initial pressure from 0
Energies 2021, 14, 4916 19 of 54

to 0.7 MPa was shown to decrease the bio-oil yield from 48.8 wt% to 8.6 wt%. Xu et al. [96]
conducted a process gas study using 2 MPa initial pressure of H2 and N2 for liquefaction
of pulp paper sludge and recorded that in the presence of a Ca(OH)2 catalyst at 280 ◦ C, the
yield of heavy oil was twice in case of H2 when compared to an inert N2 system. Singh
et al. [77] examined the reaction environment of N2 , O2 , and CO2 for liquefaction of rice
straw and observed the highest yield of bio-oil in the N2 environment and the lowest in the
presence of O2 . The oil obtained in the presence of O2 showed a higher aliphatic proton
content whereas the oil in the presence of N2 and CO2 was rich in aromatic proton contents.
All the parameters are interlinked from the standpoint of mass production, as dis-
cussed in Elliot et al. [10]. To commercialize a continuous system, we need a small reactor
size, which can effectively handle high concentrated feed at high temperatures and have
low residence time to achieve required conversion. At high temperatures, pressure is
necessary to maintain a single-phase system in the reactor. The operating pressure selected
should be able to maintain a single phase so that the liquid water slurry can be easily trans-
ported in a continuous HTL system. Hence, pressure is an important factor to maintain a
single-phase system for the reaction to progress smoothly.

2.3. Retention Time

The term retention time, also known as residence time, is defined as the period during
which the reactor is maintained at the required temperature, i.e., not including the heating
and cooling, as shown in Figure 7.

Figure 7. Heating and cooling cycle of the reactor for HTL at 300 ◦ C for 0 and 15 min retention time
(adapted from [24]).

Retention time affects most major outcomes, such as biomass conversion, yield of
products, and composition. The selection of optimum retention time depends on many
parameters, mainly temperature, heating rate, and catalysts. Using a low heating rate
means it will take longer to reach the final temperature, which provides more time for
biomass conversion and oil formation, ultimately reducing the need for a longer retention
time. Similarly, the hydrolysis takes place faster in the critical temperature zone and in the
presence of alkalis, reducing the need for an increased retention time.
Many studies have been conducted to determine the effect of retention time over a
wide range of biomass, as reviewed in Table 5. Xu et al. [96] conducted an HTL of secondary
pulp/paper sludge at 280 ◦ C, without a catalyst, for a retention time of 15–120 min and
observed that a yield of heavy oil increased with the increase in time and that the water-
soluble organics decreased. It was thought that the increased time allowed carbohydrates
and formic/acetic acids from the WSO to dehydrate, adding to the HO mass fraction.
During the HTL of wood, Ogi et al. [88] found that the maximum yield of oil was obtained
Energies 2021, 14, 4916 20 of 54

at 0 min (24.6 wt%) and the yield of oil decreased continuously afterwards, up to 180 min
(14.7 wt%). Similarly, Qu et al. [89] found a decrease in bio-oil with an increase in retention
time for the HTL of Cunninghamia lanceolate, which was mainly due to condensation
and the repolymerization of intermediates to form solid products as a result of prolonged
exposure of intermediates to high temperature. Later, Yang et al. [79] observed that a
10-min retention time was adequate to break down biomass and achieve the highest yield
of crude bio-oil. A further increase in the retention time resulted in the decomposition of
crude bio-oil into lighter products and gases.
In contrast to the above outcomes, several other studies support longer retention times,
finding that they are more favorable in increasing the yield. Yang et al. [97] examined the
liquefaction of birch powder with a methanol solvent for a retention time of 10 to 480 min
above the supercritical condition of methanol and found that the conversion and yield
of all gas, heavy oil, and water-soluble organics increased with an increase in reaction
time. Yang et al. [89] also concluded that sub/supercritical alcohol readily dissolves the
unstable liquid intermediates, which ultimately prevents the heavy oil from condensing
into char. Yim et al. [103] explored the effect of retention time on the relative yield of
bio-oil in the presence of four metal oxide catalysts (La2 O3 , CeO2 , CaO, and MnO) at
390 ◦ C. He found that the relative yield of bio-oil increased on increasing retention time
from 15 min to 60 min, indicating that the cleavage of C–C bonds in biomass led to the
dehydration, decomposition, and recombination of fragments that were added to the bio-
oil. However, a prolonged time—between 60 and 960 min—resulted in a decrease in the
relative bio-oil yield, mainly due to cracking of bio-oil in low molecular gaseous products,
and repolymerization of intermediates into solid char. A short retention time can lead to
the incomplete decomposition of biomass, whereas a longer-than-needed retention time
can promote repolymerization/carbonization and the cracking of oil and organics into char
and gas, along with an increase in operational costs.

2.4. Heating Rate

The heating rate, defined as the rate of temperature increase per unit time, is another
important parameter during liquefaction. Figure 7 shows the heating and cooling cycle for
the HTL batch reactor. As shown in Figure 7, the heating cycle for an electrically heated
batch autoclave reactor can be divided in two zones. Zone A and B have a heating rate of
10 ◦ C min−1 and 2.5◦ C min−1 , respectively [24]. In general, biomass spends a larger part
of the heating period in a high subcritical temperature range (Zone B) before reaching the
desired reaction temperature. Thus the majority of the reactions that occurred during the
HTL process were completed during the long heating cycle [81].
The studies that look at the effect of the heating rate on the HTL of wood and agri-
cultural biomass, as shown in Table 6, are very limited when compared to other tech-
niques of bio-oil production, such as pyrolysis. In pyrolysis, the heating rate is a well-
established parameter affecting the yield of products. Tran et al. [104] used a heating rate of
66–179 ◦ C min−1 at 350 ◦ C to determine trends in the bio-oil yield from spruce wood; the
results indicated a positive trend of a continuous increase in bio-oil yield with an increase
in the heating rate, whereas the yield of the solid residue decreased. Zhang et al. [72,90]
performed liquefaction of corn stover, aspen wood and high diversity grassland perennials
and found that heating rate was a major parameter affecting the yield of liquid products,
although there was no significant effect on the composition of liquid products. Corn stover
and aspen wood were heated to 350 ◦ C (20 MPa) at a rate of 5–140 ◦ C min−1 , whereas
grassland perennials were heated to 375 ◦ C (22 MPa) at the same rate. It was found that the
liquid yield increased for corn stover and aspen wood by approximately 20 wt% and for
grassland perennials by 12 wt% when the heating rate increased. The cooling rate shows
no significant effect on product yield.
Energies 2021, 14, 4916 21 of 54

Table 5. Effect of retention time on HTL operation.

Process Product HHV * C* H* O*

Feedstock Condition Yield wt%, (MJ kg−1 ) (wt%) (wt%) (wt%) Comments/Findings Ref.

Rt *:
Wood 0–180 min HO *: Highest oil yield was obtained at 0 min
T *: 350 ◦ C, 14.7–24.6 30.3–35.8 71.6–77.9 6.9–7.9 14.1–21.5 [88]
(konara) and yield decreased afterwards.
Pi : 2 MPa
Optimum time was 10 min and the
Cunninghamia Rt : 10–30 min HO: CHNS and HHV values are mentioned for
T: 320 ◦ C 17.5–23.8 28.9 73.3 5.6 21.1 the same. [89]
lanceolata The yield of oil decreased with
retention time.
Rt : Total conversion and yield of all
10–480 min HO: 10–26 - - - -
Birch powder T: 300 ◦ C, products increased monotonically with [97]
methanol retention time.

Rt : 5–60 min BO *: 10–23 31.0–33.7 66.6–69.2 8.6–9.6 17.5–22.8

T: 200 ◦ C The effect of retention time was more
Microalgae pronounced at lower temperature
(Desmod- (200 ◦ C). The effect of time was little at [73]
esmus Rt : 5–60 min BO: 34.9–35.8 72.4–75 8.8–9 10.2–12.3 300 ◦ C and above.
sp.) T: 300 ◦ C 40.5–46.6 Water-soluble organics decreased with
reaction time above 300 ◦ C.
The yield of bio-crude increased from
Rt : 0–120 min 0 min to 60 min and decreased
Spirulina 350 ◦ C, BC *: 34.1–36.8 73.1–77.2 8.6–9.6 9.1–11.1 afterwards. WSO fraction decreased with
20% solid 30–39.9 increase in time. [74]
platensis
concentration There was no significant effect on
solid residue.
LO *: ~4–6 22.5–23.9 59.9–61.3 5.8–6.3 32.2–34 The total bio-oil yield was maximum at
Cornelian Rt : 0–30 min 0 min retention time for 250 ◦ C and [76]
cherry stones T: 300 ◦ C 300 ◦ C, whereas at lower temperature of
HO: ~14–22 25.6–28.4 59.2–67.2 7.1–7.9 25.1–32.3
200 ◦ C it was maximum at 30 min.

Rt : It was observed that retention time had

Litsea cubeba BO: limited effect on the product yield making
30–120 min 53.5–56.9 - - - - [57]
seed T: 290 ◦ C it a thermally controlled process.
Rt : 5–30 min The highest yield of crude bio-oil was
Spent coffee BC:
T: 275 ◦ C, Pi : 22.7–31.7 31 71.2 7.1 18.7 obtained at 10 min (31.7 wt%) followed by [79]
grounds 2 MPa a decrease until 30 min (22.7 wt%).
The CHNS and HHV value was provided
Blackcurrant Rt : 0–240 min at 300 ◦ C and 60 min.The holding time
T: 300 ◦ C BO: 22.5–27 35.9 73.3 9.6 13.6 [81]
pomace had no significant effect on the yield
of products.
The maximum bio-oil yield was obtained
at residence time of 15 min.
Waste Rt : 0–60 min BO: The yield of solid residue decreased
furniture T: 280 ◦ C 7.2–12.7 - - - - [38]
sawdust initially until 30 min and increased
thereafter, whereas the gas yield increased
with increase in retention time.
The relative yield of bio-oil increased
Rt : throughout retention time for T: 360 ◦ C.
Empty fruit 15–120 min The relative yield of bio-oil increased until
T: 360–450 ◦ C - - - - - [103]
bunch 60 min for temperatures 390 and 450 ◦ C,
P: 25 MPa and decreased steeply on further increase
in time.
The yield of bio-oil and solid residue
Olive oil Rt : 5–60 min BO: increased from 5 to 15 min and decreased
29.1–32.2 68.0–70.7 7.3–8.3 20–23.7 afterwards. The carbon percentage and [85]
residue T: 300 ◦ C 20.7–30.8
HHV value of bio-oil was maximum at
residence time of 5 min.
* HO: heavy oil, BO: bio-oil, BC: bio-crude, LO: light oil, HHV; higher heating value, C: carbon, H: hydrogen, O: oxygen;, T: temperature,
Rt: retention time.
Energies 2021, 14, 4916 22 of 54

Table 6. Effect of heating rate in HTL process.

Process Product
Type Feedstock Comments/Findings Ref.
Condition Yield wt%
LP *: Liquid yield (%)
Corn stover 5–140
◦C 53.4–70.6 = (0.051 × ln( Heating rate) + 0.4532) × 100
min−1
[72]
Aspen wood T *: 350 ◦ C LP: Liquid yield (%)
50.3–72.4 = (0.0627 × ln( Heating rate) + 0.4239) × 100
High diversity 5–140
◦C LP: Liquid yield (%)
grassland min−1 [90]
61.1–73.1 = (0.0042 × ln( Heating rate) + 0.5514) × 100
perennials T: 375 ◦ C
Wood
Maximum bio-crude was obtained by a combination of fast
3–20
Red pine ◦ C min−1 BC *: heating rate, high final temperature, and immediate
[58]
sawdust 15–27 quenching.There was no effect of heating rate in the
T: 350 ◦ C
presence of supercritical EtOH.
The bio-oil yield increases with increasing heating rate,
66–179
◦C BO *: whereas the solid residue decreases.
Spruce wood min−1 [104]
18.9–35.8 Maximum yield was obtained at heating rate of
T: 350 ◦ C
179 ◦ C min−1 .
146–585
Laminaria ◦C BO: Fast heating rate promoted bio-oil yield and decreased
min−1 [105]
saccharina 53–79 formation of gas and char.
T: 350 ◦ C
Algae
BO:
Chlorella 10–25
◦ C min−1 35.8 There was no significant effect of heating rate on the yield
[106,107]
of bio-oil.
Nannochloropsis T: 350 ◦ C BO:
34.3
* BO: bio-oil, BC: bio-crude, LP: liquid products, T: temperature.

Brand et al. [58] performed a detailed experimental study to understand the effect
of the heating rate (2–20 ◦ C min−1 ) on liquefaction of sawdust for a temperature range
of 250–350 ◦ C in the presence of H2 O and EtOH as solvents. It was observed that in the
presence of H2 O solvent and for a final temperature of 250 ◦ C, yield of bio-crude was more
at a heating rate of 2 ◦ C min−1 (8 wt%) than that at 20 ◦ C min−1 (5 wt%). At a higher
temperature of 350 ◦ C, the bio-crude yield at 2 ◦ C min−1 (15 wt%) was significantly lower
than that at 20 ◦ C min−1 (27 wt%). It suggests that the optimum heating rate is linked
to the operation temperature. For a final temperature of 250 ◦ C, when compared to a
fast-heating rate, a slow heating rate provides more time for the solvent to interact with the
lignocellulose, yielding a slightly higher conversion and more bio-crude. Furthermore, for
a higher temperature of 280 to 350 ◦ C, the conversion and bio-crude yield remained mostly
unchanged with the heating rate, which could be because of the simultaneous hydrolysis
of biomass and the repolymerization of intermediates at high temperatures. The effect of
the heating rate in the presence of EtOH was negligible; a plausible explanation may be
that the supercritical state of EtOH in the temperature range had a stronger effect than the
heating rate.
Heating rate is a prominent factor, which needs to be accounted for, along with the
operation temperature and retention time. A slow heating rate may be better for a lower
subcritical temperature operation, whereas a fast-heating rate may be better for higher
subcritical and supercritical temperature operations. In the case of high temperature
operations, a slow heating rate may end up promoting many secondary reactions, such as
the repolymerization/carbonization of intermediates and bio-oil fractions to char, whereas
processes with significantly high heating rates can prompt secondary cracking of long chain
hydrocarbons and aromatics, resulting in the formation of gaseous products. In general,
the optimum temperature range for HTL lies between 300 and 350 ◦ C; a moderate-to-fast
heating rate suitably increases the kinetics for hydrolysis, dehydration, and fragmentation
Energies 2021, 14, 4916 23 of 54

and limits radicalization and repolymerization in the given temperature range. The current
literature does little to enhance our understanding of how heating rates affect lignocellulosic
biomass HTL, bio-oil yield, and reaction mechanisms. More intensive and detailed studies
are needed.

2.5. Biomass-to-Solvent Ratio

The term biomass-to-solvent ratio is also known as feed ratio. As the majority of
the experiments are conducted using water, feed ratio is more commonly known as
biomass-to-water ratio. Some studies have defined it in a reciprocal form and called
it the water/solvent-to-biomass ratio [38,79]. For the HTL of lignocellulosic biomass in a
batch process, it is logical to define the feed ratio as the biomass-to-water ratio, whereas in
continuous processes where a pretreated concentrated slurry is supplied to the processing
system, it is more commonly referred to as a solid concentration (wt% or mass fraction) or
reactor loading.
Feed ratio is an important parameter and needs to be controlled in a certain desired
range to obtain a higher conversion and maximize bio-oil yield. Water is essential for
solvolysis, to act as a solvent medium. In cases where the biomass-to-water ratio is very
low, the yield will be low as the carbon entering the system will be low, whereas the cost
of operation (heating) will be high because of the need to raise the water temperature to
the desired level. For the biomass-to-water ratio where the solid concentration is very
high, not enough H+ and OH− ions will be available to support the hydrolysis of the
lignocellulosic biomass. Furthermore, the high solid concentration directly impacts the cost
of the process because of the need for intense pumping, a better mixing and turbulence
facility, and improved heating supply. Higher solid loading increases the bio-oil yield and
reduces carbon losses in the system [10].
Some of the research focused on feed ratio is discussed in Table 7. Akhtar et al. [108]
performed liquefaction of an empty palm fruit bunch at 270 ◦ C and 1.0 M K2 CO3 for a feed
ratio (biomass-to-water) of 1/10–8/10 g mL−1 ; the study suggested that increasing the feed
ratio from 1/10 to 2/10 g mL−1 increased the conversion and liquid yield. A further increase
of the feed concentration drastically decreased the biomass conversion and product yield. In
many other studies, it was observed that, after a point with the increase in the concentration
of biomass, there was a decrease in the yield of bio-oil [57,81,89]. The low concentration
of aqueous solvent in cases of high feed concentration makes it difficult for a solvent to
dissolve the biomass. The low degradation of biomass due to the solvent’s poor dissolution
power leads to a decrease in conversion and yield. In highly concentrated feed, unconverted
biomass must compete with other intermediate hydrolysis reactions for water, leading to
an increased intermediate concentration in the aqueous phase and bio-oil. This increased
intermediate concentration results in a higher probability of repolymerization reactions,
leading to a higher solid residue formation [81]. Moreover, a very high solid amount, with
respect to the available water, can limit the availability of water for solvolysis and the
hydration process, resulting in poor and incomplete degradation of the lignocellulosic
biomass, leaving behind unconverted solid residue [96]. Wang et al. [57] performed HTL of
Litsea cubeba seed powder at different reactor loading concentrations and observed that,
with an increase in the reactor loading from 0.5 to 4.5 g, the yield of the gases decreased
from 40% to 19.6%. The decrease in the gas fraction was linked to the high-pressure
build-up in the reactor caused by higher reactor loading.
Energies 2021, 14, 4916 24 of 54

Table 7. Effect of the feed ratio in HTL process.

Process Product HHV * C* H* O* Comments

Feedstock Condition Yield (wt%) (MJ kg−1 ) (wt%) (wt%) (wt%) Ref.

1/16–1/6
g/mL Yield of oil was maximum
Wood HO *:
(konara) T *: 300 ◦ C, 16.4–25.2 31.9–33.8 73.8–76.6 7.16–7.48 15.9–19 at 5/50 g/mL of [88]
Pi *: 2 MPa biomass/water ratio.
Rt *: 30 min
8/100–
12.5/100 The fraction of heavy oil
Cunninghamia HO:
g/mLT: 16.3–23.8 - - - - decreased with increasing [89]
lanceolata 320 ◦ C, biomass/water ratio.
Rt : 10 min
Secondary 4.8–16.7 wt% There was a significant
solid HO:
pulp/paper concentration - - - - decrease in water-soluble [96]
sludge + T: 280 ◦ C, 15–22 organics with increased
newspaper Rt : 60 min feed concentration.
Phenols (0.6–60.0), methyl
ester (0–94.3%), benzoic
1/10–8/10 acid (0–24.3%)
Empty palm g/mL With increase in feed
LP *:
T: 270 ◦ C, 50–68 - - - - concentration fraction of [108]
fruit bunch Pi : 2 MPa, methyl esters decreased
Rt : 20 min initially and on further
increase vanished
completely.
Bio-crude yield increased
10–50% solid as solid concentration
Spirulina concentration BC *: increased from 10 to 20%.
35.6–35.9 72.3–73.8 8.9–9.1 10.5–11.7 [74]
platensis 350 ◦ C, 33–39.9 No change in product
Rt : 60 min composition over solid
concentration of 20%.
The bio-oil yield increased
0.5–4.5 g BO *:
Litsea cubeba T: 290 ◦ C, 40.8 76.2 11.9 10.4 initially with solid fraction [57]
seed powder Rt : 60 min 42.4–56.9 and started to decrease
afterwards.
2/5–1/15 HO:
Miscanthus T: 410 ◦ C, Rt : 9–22 - 77 6.9 16 - [78]
60 min
1/20–1/5 Larger water to spent coffee
Spent coffee g/mL BC: ground ratio has positive
T: 275 ◦ C, 35.3–47.3 31 71.2 7.1 18.7
impact on conversion rate [79]
grounds Pi : 2 MPa,
Rt : 10 min and bio-oil yield.
Carbon recovery in bio-oil
0.05–0.29 (dry increased initially with
Blackcurrant mass fraction) BO: increase in concentration
- - - - [81]
pomace T: 300 ◦ C, 24–29 and decreased after a point,
Rt : 60 min whereas the yield of bio-oil
decreased thoroughly.
* HO: heavy oil, BO: bio-oil, BC: bio-crude, LP: liquid products, HHV; higher heating value, C: carbon, H: hydrogen, O: oxygen; Pi : initial
pressure, Pf : final pressure, T: temperature, Rt : retention time.

3. Effect of Catalysts and Solvents

3.1. Effect of Catalysts
Over the last two decades, many researchers have focused on the effect of catalysts, as
summarized in Table 8. The effects of different catalysts on the overall product yield, quality,
and biomass decomposition are provided in Table 9. In most of the cases, the catalyst
plays a promising role in increasing the bio-oil yield and improving its properties. It also
triggers earlier and faster biomass degradation and hinders secondary reactions, such as
repolymerization and cracking, activating kinetics of reactions and reducing dependency
on pressure, temperature, and retention time. The two classes of catalysts used in the HTL
operation are homogeneous and heterogeneous. These classes are discussed in detail in the
following sections.
Energies 2021, 14, 4916 25 of 54

Table 8. Some major HTL studies focused on understanding the effect of catalysts.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Catalytic activity order K2 CO3 > KOH > RbCO3
Low temperature catalytic hydrothermal >RbOH > Na2 CO3 > NaOH > CsCO3 > CsOH for
treatment of wood biomass: analysis of bio-oil production.
1 2005 liquid products. Oil yield increased from 8.6 wt% in water to [70,109,110]
Effect of Na and K hydroxides and 33.7 wt% in the presence of K2 CO3 .
carbonates on liquefaction products. Boiling point of hydrocarbons ranged near n-C11
and mainly phenolic in nature.
Both Fe and Na2 CO3 effectively enhanced the
Direct liquefaction of paulownia in hot formation of heavy oil, and the highest heavy oil
compressed water. yield of 36.34 wt% was observed with Fe catalyst
2 2010 [41]
Effect of Fe and Na2 CO3 on heavy at 340 ◦ C.
oil yield. Both catalysts significantly promoted the
gases formation.
The total bio-oil yield at 300 ◦ C, 0 min without
HTL of beech wood using a natural and with colemanite was 21 wt% and 41 wt%.
3 2012 [43]
calcium borate mineral. The use of colemanite had no significant effect on
heating value and composition of oil.
The highest heating value of resulting heavy oil
Effect of sodium perborate monohydrate
was 32 MJ kg−1 , at 350 ◦ C with the catalyst.
4 2013 concentrations on product distributions [111]
The product distribution significantly varied with
from HTL of scotch pine wood.
temperature and additive concentration.
Addition of K2 CO3 increased bio-crude yield and
Influence of alkali catalyst on product
inhibited solid char formation.
5 2015 yield and properties via HTL of [15]
Catalyst run bio-crude has better properties, such
barley straw.
as higher HHV value and lower O/C ratio.
The highest bio-oil yield was 13.9 wt% at 300 ◦ C
Characterization of HTL products from without the catalyst, where the water content was
coconut shell in the presence of selected minimum (3 wt%) and HHV was highest
transition metal chlorides. (31.1 MJ kg−1 ).
6 2016 [93]
To examine the effect of Zn, Cu and Ni on Main decomposition products of cellulose
HTL at fixed temperature and to levulinic acid and γ-valerolactone were present
understand the effect of temperature. in oil.The use of transition metals helped in
decreasing the TAN value of oil.
Structural analysis of bio-oil from Conversion increased with increase in
subcritical and supercritical HTL of temperature. Colemanite catalyst was more
7 2016 Datura stramonium L. plant stems. effective than Borax. [36]
Understanding the effect of temperature The GC–MS composition at all of the
and catalyst (colemanite and borax). temperatures were provided.
The use of water tolerant Lewis acids had
negative effects on bio-oil yields.
The effects of water tolerant Lewis acids The study suggest that low catalyst concentration
8 2016 [37]
on the HTL of lignocellulosic biomass. promotes production of oil.
Lewis acids have no significant effects on
composition of oil.
Production of bio-oil via HTL of
The highest yield of bio-oil (54.1 wt%) was
birch sawdust.
obtained at 300 ◦ C, 5 min in the presence of
To understand the effect of
NaOH catalyst.
9 2017 biomass/water ratio, temperature, H2 [34]
The order of catalyst to promote bio-oil yield was
pressure, residence time, catalysts (FeSO4 ,
NaOH > Na2 CO3 > Ni65% |SiO2 –Al2 O3 > Raney
ZnSO4 , NiSO4 , Raney nickel, Ni65%
nickel > NiSO4 > ZnSO4 > FeSO4 > none.
-Al2 O3 , Na2 CO3 , NaOH).
The tested catalyst (NiO) helped in increasing the
HTL of rice straw with NiO nanocatalyst
10 2017 overall oil yield but had no significant impact on [26]
for bio-oil production.
the elemental composition and HHV of oil.
Energies 2021, 14, 4916 26 of 54

Table 8. Cont.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

The addition of catalysts was conducive for
bio-oil yield and quality.
All (Co, Ni, and Pt) gave almost equal bio-oil
Catalytic HTL for bio-oil production over
yield of 40.25 wt%, whereas the conversion of
carbon nanotubes (CNTs) supported
biomass was highest for Co|CNTs (95.8%) > Ni
metal catalysts.
11 2017 (93.3%) > Pt (92.4%) > None (~89%). [112]
Effect of carbon nanotubes supported
Bio-oil obtained using Co catalyst had higher
transition metals (Co, Ni, Pt) for HTL of
hydrocarbons, lower fatty acids, and
Dunaliella tertiolecta to produce bio-oil.
nitrogen compounds.
The selected catalysts helped in reducing the
nitrogen content in bio-oil.
The highest bio-crude yield was obtained with
K2 CO3 (61.8 wt%) catalyst.
Bio-crude from pretreated sorghum
The bio-crude had high carbon content and low
bagasse through catalytic HTL.
12 2017 nitrogen and sulfur contents. [29]
To study liquefaction at different
The relative high oxygen content ~15% in
temperature and six different catalysts.
bio-crude requires it to be upgraded before
refinery ready.
It was found that La2 O3 , CeO2 , MnO and CaO,
Metal oxide catalyzed hydrothermal
were four most active catalyst.
liquefaction of Malaysian oil palm
The bio-oil yield in case of CeO2 was 1.44 times
biomass to bio-oil under
that of without catalyst.
supercritical condition.
13 2017 It was found that phenolics, ketones, other [103]
Effect of CaO, MgO, MnO, ZnO, NiO,
aromatics, and carboxylic acids were the
SnO, CeO2 , Al2 O3 , La2 O3 was studied.
major compounds.
Fitting kinetic formation to the modified
The bio-oil produced was easily volatilized and
Reverchon-Sesti Osseo model.
combusted in TGA study.
Oxidation of Fe to produce H2 in water was a key
Enhanced bio-crude yield and quality by step in the process as the produced H2 prevented
reductive HTL of oak wood biomass: the repolymerization and condensation of
Effect of iron addition. bio-oil precursors.
14 2019 [31]
Iron powder, hematite, and magnetite Fe as catalyst increased the bio-oil yield by
were investigated as catalyst in 1:5 30 wt% and improved the quality by reducing
biomass to water ratio for 260–330 ◦ C. oxygen content, increasing the HHV value to
32.4 MJ kg−1 .
Fe was found to be most effective for the
Catalytic HTL of lactuca scariola with a
production of bio-oil.
15 2020 heterogeneous catalyst. [84]
The yield of aqueous and gas fraction was
Effect of Zn, Fe, and Zn + Fe was studied.
maximum in the presence of Zn + Fe.
HTL of olive oil residue It was found that the yield of bio-oil decreased
16 2021 Understanding the effect of metal and that of solid residue increased with the [85]
chlorides on HTL products. addition of AlCl3 and SnCl3 .
It was found that the catalyst had a negative
Use of Lewis acid, a Brønsted acid, and effect on the yield of bio-oil; moreover, the yield
their binary mixtures for the HTL of of oil was found to decrease with the increase of
lignocellulose.HTL of teak wood was catalyst loading.
17 2021 [113]
studied without and with the use of The use of catalyst increased the percentage of
Mg(ClO4 )2 , HClO4 , and naphtha in bio-oils.
HClO4 /Mg(ClO4 )2 . The relative yield of ketones, phenols, and acids
were affected in the presence of the catalyst.

3.1.1. Homogeneous Catalysts

A wide range of homogeneous catalysts is used for the process of liquefaction. These
include hydroxides and carbonate salts of alkali, such as NaOH, Na2 CO3 , KOH, and
K2 CO3 , and many acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, and
Energies 2021, 14, 4916 27 of 54

acetic acid. Both the hydroxide and carbonates of alkali metals are found to greatly increase
the degradation of biomass in a water medium, giving a higher liquid product yield. In a
series of literature, a detailed analysis on the efficacy of alkali and alkaline earth metal salts
in a water medium for liquefaction of lignocellulosic biomass was presented by Karagoz
et al. [69,105,106]. The catalysts can be arranged according to their decreasing effect on
the yield of total bio-oil: K2 CO3 > KOH > RbCO3 > RbOH > Na2 CO3 > NaOH > CsCO3 >
CsOH > Ca(OH)2 > none. In the case of K2 CO3 as a catalyst, the total bio-oil yield increased
from 8.6 wt% (thermal run) to 33.7 wt% and the solid residue decreased from 41.7 wt%
(thermal) to 4.0 wt% (K2 CO3 ). Later the effect of alkali was considered by many other
groups, K2 CO3 [108], Na2 CO3 [114], NaOH [115], KOH [116]. Tekin et al. [43] inspected
the usefulness of potassium tert-butoxide (t-BuOK) and KOH on the liquefaction of scotch
pine wood and found that the catalyst had a negligible effect at 250 ◦ C, while the yield of
bio-oil significantly increased in the presence of a catalyst at 300 ◦ C and 350 ◦ C.
To understand the effect of a catalyst in a solvent other that water, Khampuang
et al. [94] investigated the effect of NaOH (10 wt%) and KOH (10 wt%) on the liquefaction
of corncobs in an ethanol (100%) solvent. The result showed a steep increase in bio-oil
yield from 38.6 wt% (no catalyst) to 50.5 wt% (NaOH) and 55.6 wt% (KOH), adding to the
practicality of alkali for HTL in alcohol solvents, too. In many cases, feedstock is pretreated
in an alkaline medium instead of adding a catalyst to the reactor medium. Liu et al. [39]
compared the yield of bio-oil from un-pretreated cypress (27.5 wt%) and alkaline pretreated
biomass (44–48 wt%) at 300 ◦ C and observed significant increase in the yield of bio-oil in
the case of the alkaline-pretreated feedstock.
Akhtar et al. [108] studied the effect of various concentrations of K2 CO3 (0.1–2.0 M)
at 270 ◦ C, 2 MPa, 20 min for a biomass-to-water ratio of 5 g/25 mL, as shown in Figure 8.
They observed a significant increase in biomass degradation, mass conversion, and oil yield
as the concentration increased from 0.1–1.0 M, followed by a steep decrease in biomass
degradation and oil yield on increasing the catalyst concentration from 1.0–2.0 M. One
possible explanation for the impeded liquid yield may be the repolymerization of small
chain molecules at a higher concentration. Many other studies investigated the effect of
catalyst concentration and found an increase in bio-oil yield up to a certain concentration
as shown in Figure 8. This increase was followed by a decrease in yield after the catalyst
concentration was increased further [111,117].

Figure 8. Effect of homogeneous catalyst concentration (alkali) on the yield of bio-oil.

Potassium carbonate is by far the most effective alkali catalyst to increase the yield of
bio-oil in the optimum temperature range of 280–350 ◦ C. The K2 CO3 reacts with water to
Energies 2021, 14, 4916 28 of 54

form hydroxide and bicarbonate, which promotes the reaction pathway by acting as an
intermediate [27], as shown below.

K2 CO3 + H2 O → KHCO3 + KOH; (7)

2KHCO3 → H2 O + K2 CO3 + CO2

The alkaline medium changes the reaction behavior of biomass and promotes the
weakening of intramolecular interactions in glucoside bonds in the biomass, resulting
in a decrease of the activation energy for complex reactions and reducing the thermal
stability of stable chemical structures [15,94]. Furthermore, it disrupts the physical barriers
in biomass, giving rise to the absorption of the solvent in the biomass. This causes a broader
separation between the structural linkages in cellulose and lignin, which increases the
surface availability to the interior structure and enhances the degradation [39,42]. Hence,
when used in reasonable concentrations, alkali catalysts are advantageous to the HTL
process and to increasing the bio-oil yield.

3.1.2. Heterogeneous Catalysts

Heterogeneous catalysts are also extensively studied for their application in the HTL
process. Some of the main elements considered for use as catalysts are Fe [118], Cu [119],
Ni [120], Al [121], Zn [122], Co [123], Pt [112], Mn, Ce, and Sn [103], either in their ox-
ide, chloride, or sulfate form. Common supports used in the studies include Si-Al [29],
Al2 O3 [124], SBA−15 [121], MCM-41 [125], carbon nanotubes (CNTs) [112], HZSM-5 [123],
and zeolites [29]. In studies, many minerals, such as colemanite [66], hydrotalcite [66],
hematite [125], magnetite [31], and borax [36], found in local regions, are also investigated
to understand their effect on the HTL process.

Table 9. Effect of catalyst during HTL process.

Process Product HHV * C* H* O*

Feedstock Condition Catalysts Yield (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.
(wt%)

T *: 350 ◦ C - HO *: 5.0 28.9 70.9 6.9 22.1 -

Wood [88]
(konara) Pi *: 2 MPa HO:
Rt *: 30 min K2 CO3 30.4–33.4 71.8–76.6 6.8–7.7 15.9–21.2 -
21.4–26.2
EEO *: aldehydes (18%),
ketones (8%), phenolics (45%),
- BO *: 8.6 - - - - fatty acids (8%)
EAO *: unsaturated chain
(26%), ketones (11%),
-oic acid (32%)
NaOH BO: 22.4
Sawdust T: 280 ◦ C [70,109]
(pine wood) Rt : 15 min Na2 CO3 BO: 23.0
EEO: acetic acid (3–12%),
KOH BO: 28.7 phenolics (50–70%),
- - - - benzenediols (10–25%)
K2 CO3 Total oil:
33.7 EAO: ketones (45–60%),
unsaturated chains (15–25%)
RbOH BO: 23.8
CsOH BO: 20.8
- LP *: 30 - - - - Methyl esters (26.44%)

NaOH LP: ~58 - - - - Phenols (6%),

T: 270 ◦ C methyl ester (86.45%)
Empty palm Pi : 2 MPa [108]
fruit bunch Rt : 20 min Phenols (18.4%),
KOH LP: ~58 - - - -
methyl ester (81.6%)

K2 CO3 LP: ~63 - - - - Phenols (60.08%),

methyl ester (39.92%)
Energies 2021, 14, 4916 29 of 54

Table 9. Cont.

Process Product HHV * C* H* O*

Feedstock Condition Catalysts Yield (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.
(wt%)
Phenolics (37%), ketones (13%),
T: 300 ◦ C carboxylic acid/ester (17%),
- HO: 26 26.3 - - -
Rt : 10 min
phenyl derivatives (3%)
Phenolics (39%), ketones (17%),
T: 300 ◦ C carboxylic acid/ester (7%),
Wood Na2 CO3 HO: 31.5 28.1 - - -
Rt : 10 min [41]
(Paulownia) phenyl derivatives (10%)
Phenolics (38%), ketones (20%),
T: 340 ◦ C carboxylic acid/ester (6%),
Fe HO: 36 31.5 - - -
Rt : 10 min phenyl derivatives (3%), long
chain alkanes (2%)
- BO: 24.9 29.5 70.5 6.8 22.4 -
Pulp/paper KOH BO: 31.2 29.5 70.2 6.9 22.4 -
mill sludge + T: 300 ◦ C [75]
Rt : 20 min HCOOH BO: 34.4 29.5 69.9 6.9 22.1 -
newspaper
waste FeS BO: 27.7 29.9 71.4 6.7 21.4 -
Furfurals (13%), ketones
LO *: 6.2 22.9 60 6 34 (12.7%), phenolics (22%),
benzenediols (5.2%)
- Acetic acid (2%), ketones
Beech T: 300 ◦ C HO: 14.8 24.4 60 7 33 (6.4%), phenolics (11.3%),
FAAE * (3%) [43]
wood Rt : 0 min
Ketones (12%), phenolics
LO: 11.1 21.2 59.6 6.6 36.4
Colemanite (29.4%), benzenediols (7.3%)

HO: 29.8 25.2 62.5 6.7 31 Acetic acid (2%), ketones

(21.8%), phenolics (14%)

LO: 4.5 22.9 60 6.1 33.9 Furfurals, ketones,

phenolics, FAAE
-
Ketones (16%), phenolics
HO: 19 27.1 66.6 6.6 26.8
Scotch pine T: 300 ◦ C (9.6%), FAAE (18)
[43]
wood Rt : 0 min
Acetic acid, ketones, phenolics,
LO: 7 24.2 61 6.6 32.5
phenyl derivatives, FAAE
NaBO3 ·H2 O
Ketones (60), phenolics (4.4),
HO: 33 28.6 68 7.1 24.9
FAAE (9%)
Hexadecanoic acid (54%),
- BO: 14.2 33.1 79.4 6.3 13.3 6-octadecanoic acid (21.3%),
oleic acid (26%)

K2 CO3 BO: 27.9 34.4 80.7 6.7 11.8 Benzenediols (51%), catechols
(24%), dihydroxytoluene (13%)
Oil palm T: 330 ◦ C [42]
shell Rt : 60 min Benzenediols (52%), catechols
Na2 CO3 BO: 26.3 32.9 76.5 7.1 15.9 (24.5%), ethylene oxide (18%),
methyl tetradecanoate (13%)
Benzenediols (73%), catechols
NaOH BO: 23.9 31.1 69.9 8 21.5 (16.4%), dihydroxytoluene
(8.3%), ethylene oxide (2.3%)
BO:
- - - - -
27.5–31.1 Ethanol insoluble organics,
Cypress T: [39]
260–300 ◦ C ethanol soluble organics, DEE
Alkaline BO:
- - - - soluble and insoluble oil
pretreated 29.7–48.4
Phenolics + alcohols (12.6%),
- BC *: 17.88 24.9 62.6 6.4 29.8 ketones (13%), -oic acids (29%),
aldehydes (7.7%)
Barley T: 300 ◦ C [15]
straw Phenolics + alcohols (12.8%),
K2 CO3 BC: 34.85 27.3 67.9 7.6 23.2 ketones (13%), -oic acids (24%),
aldehydes (7%)

- BO: 29.7–30.9 65.6–68.4 6.7–7.4 5.5–5.6 -

Waste T: 1.2–3.7
bamboo 290–380 ◦ C [80]
chopstick Rt : 30 min BO:
K2 CO3 31.6–33.9 66.4–74.2 6.7–7.4 18.4–25.1 -
7.1–21.2
Cyclic HC * (15%), saturated
- BO: 32 - - - -
chain HC (56%), acids (13.4%)

Datura Ketones (7.2%), cyclic HC (2%),

stramonium T: 300 ◦ C Borax BO: 36 - - - - saturated chain HC (52%), [36]
L. stems acids (4.2%)
Ketones (6.7%), cyclic HC
Colemanite BO: 40.2 - - - - (0.5%), saturated chain HC
(28%), acids (5.5%)
Energies 2021, 14, 4916 30 of 54

Table 9. Cont.

Process Product HHV * C* H* O*

Feedstock Condition Catalysts Yield (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.
(wt%)
Ketones (2.5%), phenol (5%),
- BO: 13.9 31.1 - - - acids (1.7%), furfurals (6%),
polyols, and alcohols (5.3%)
Ketones (2.1%), phenol (6.3%),
ZnCl2 BO: 5–6 28.7 - - - acids (0.6%), furfurals (7.3%),
Coconut T: 300 ◦ C polyols, and alcohols (3.7%)
[93]
shell Rt : 30 min
Ketones (1.1%), phenol (5.1%),
CuCl2 BO: 2–5 24 - - - acids (0.8%), furfurals (6.8%),
polyols, and alcohols (1.7%)
Ketones (1.4%), phenol (3.7%),
NiCl2 BO: 3–5 28.3 - - - acids (0.3%), furfurals (2.4%),
polyols, and alcohols (3.4%)
Furfurals (4.6%), phenolics
- BO: 17.5 26.8 66.3 6.4 27.1
(39.1%), ketones (8.8%)
Furfurals (5.3%), phenolics
T: 300 ◦ C In(OTf)3 BO: 13.37 25.5 65 6.1 28.8
Poplar (39.5%), ketones (10.1%)
Pi : 1 MPa [37]
wood Rt : 10 min Furfurals (6.7%), phenolics
Yb(OTf)3 BO: 13.48 24.3 63.6 5.8 30.6
(38.1%), ketones (9.8%)
Furfurals (3.4%), phenolics
InCl3 BO: 12.42 24.8 64.1 5.9 29.9
(36.6%), ketones (11.8%)

Spent BC:
- 34.5 73.7 8.5 13.1 -
T: 300 ◦ C 35 ± 12
[35]
mushroom Rt : 15 min
compost K2 CO3 BC: 48 ± 9 34.1 72 8.8 14.8 -
- BC: 19.6 40.4 73.9 12.3 13 Long chain carboxylic acids
Spent coffee T: 250 ◦ C Long chain carboxylic acids, [82]
ground Rt : 10 min NaOH BC: 26.5 31.9 66.6 9.2 21.9 aldehyde, ketones,
alcohols, esters
Long chain carboxylic acids,
- BC: 20.8 27.9 67.3 6.7 25.1 aldehyde, ketones, alcohols,
T: 250 ◦ C esters, cyclic oxygenates
Corn stalk Rt : 10 min Long chain carboxylic acids,
NaOH BC: 21.4 27 64.7 6.9 27.3 aldehyde, ketones, alcohols,
esters, cyclic oxygenates
- BC: 21.4 33.3 71.9 8.5 17.9 Long chain carboxylic acids
Spent coffee
T: 250 ◦ C Long chain carboxylic acids,
ground + Rt : 10 min
corn stalk NaOH BC: 29.5 29.1 65 8.1 25.2 aldehyde, ketones, alcohols,
esters, cyclic oxygenates
Phenols (39%), ketones (21%),
LO: 11.7 24.9 61.1 6.9 31.4 alcohols (27%), alkanes (8%),
esters (3%)
-
Carboxylic acids (15.6%),
HO: 15.9 31.9 72.7 7.5 18.8 ketones (9%), alcohols (12.5%),
Rice straw T: 300 ◦C alkanes (28%), amines (9%) [26]
Phenols (41%), ketones (24%),
LO: 13.2 23.9 60.3 6.9 32.2 alcohols (27%), alkenes (2.4%),
carboxylic acids (3%)
NiO
Carboxylic acids (26.6%),
HO: 17.2 31.6 72.1 7.5 19.5 ketones (7.3%), alcohols (10%),
alkanes (36%), amines (11%)
HCs (14%), ketones (20%), fatty
- BO: 34 - - - - acids (50%), N-containing
compounds (15%)
HCs (50%), ketones (13%), fatty
T: 320 ◦ C Co|CNTs BO: 40.25 - - - - acids (25%), N-containing
Dunaliella Rt : 30 min [112]
tertiolecta compounds (8%)
P: 12 MPa
HCs (25%), ketones (8%), fatty
Ni|CNTs BO: 40.25 - - - - acids (65%), N-containing
compounds (5%)
HCss (28%), ketones (10%),
Pt|CNTs BO: 40.25 - - - - fatty acids (55%), N-containing
compounds (12%)
Energies 2021, 14, 4916 31 of 54

Table 9. Cont.

Process Product HHV * C* H* O*

Feedstock Condition Catalysts Yield (MJ kg−1 ) (wt%) (wt%) (wt%) Oil Properties Ref.
(wt%)
Ketones (3%), alcohols (1.5%),
K2 CO3 BC: 61.8 33.1 73.2 7.7 15 HCs (0.6%), phenolics (22%),
esters (3.2%), phenyl deriv. (4%)
Pretreated Ketones (4%), alcohols (0.5%),
sorghum T: 300 ◦ C KOH BC: 42.2 30 64.3 7.6 14.5 HCs (0.8%), phenolics (23%), [29]
Bagasse esters (10%), phenyl deri (1.7%)
Ketones (5%), alcohols (2%),
Ni|Si-Al BC: 45.5 21.5 50.2 5.9 21.5 HCs (2.2), phenolics (15%),
esters (2.7%), phenyl deri (4.2)
Ketones (29.4%), phenolics
- BO: 6.6 - - - -
Spruce T: 300 ◦ C (40.6%), FAAE (9.6%)
Pi : 2 MPa [124]
wood Rt : 30 min Ketones (23.7%), phenolics
KF/Al2 O3 BO: 13.9 28.42 68.3 6.8 24.8
(44.7%), FAAE (8.7%)

* HO: heavy oil, BO: bio-oil, BC: bio-crude, LO: light oil, LP: liquid products, HHV; higher heating value, C: carbon, H: hydrogen, O:
oxygen; Pi : initial pressure, Pf : final pressure, T: temperature, Rt : retention time, FAAE: fatty acid alky ester, HC: hydrocarbon; EAO: ethyl
acetate oil phase, EEO: ethyl ether oil phase.

Zhang et al. [75] studied the effect of adding homogeneous catalysts (HCOOH, KOH)
and heterogeneous catalysts (FeS) on the liquefaction of secondary pulp/paper mill sludge
at 300 ◦ C, 20 min. The reactivity order of the catalyst according to the bio-oil yield was
found to be HCOOH (34.4 wt%) > KOH (31.2 wt%) > FeS (27.7 wt%) > thermal (24.9 wt%);
there was no significant difference observed in the elemental analysis and higher heating
value of oil obtained in the presence of different catalysts. Bi et al. [29] studied various
catalysts and arranged them as per their efficacy to produce the bio-crude as K2 CO3 >
Ni/Si–Al > KOH > none. It was observed that, when compared to Ni/Si–Al run and
catalyst free run, bio-oil obtained in the presence of K2 CO3 and KOH has a significantly
high percentage of a carbon and HHV value. Caprariis et al. [31] examined the effect of Fe
powder, Fe2 O3 , and Fe3 O4 in a reducing gas (H2 ) environment and found that the highest
bio-oil yield and the lowest char was obtained in the presence of Fe powder. Fe begins to
oxidize with water over 250 ◦ C and its oxidation increases with a temperature increase.
The oxidation of Fe produces H2 gas (equation). This prevents the repolymerization and
condensation of precursors formed in water, such as 5-HMF (5-hydroxymethylfurfural),
which is responsible for bio-oil formation and, thus, reduces char formation. Fe3+ in
Fe2 O3 being in higher oxidation state failed to increase the bio-oil yield, whereas Fe2+ in
Fe3 O4 still had excellent oxidation capability and, therefore, contributed to the degradation
and dehydration of lignocellulosic components, leading to the dehydration of fructose
(isomerized glucose) and promoting the formation of 5-HMF [51,64,126].
In a study on the loading capacity of the potassium fluoride-doped aluminum oxide
(KF/AL2 O3 ) catalyst on product yield, Alper et al. [124] showed an increase in bio-oil
yield when the loading capacity increased from 10 wt% to 20 wt% as shown in Figure 9a.
This was followed by decrease in bio-oil when the loading was increased to 40 wt%. One
possible reason for the decrease in bio-oil at a high solid base concentration of a KF/Al2 O3
catalyst in HTL may be the Cannizzaro reaction. In this reaction, the aldehyde initially
produces alcohol and acid, which, on further decomposition, results in increasing the
gaseous fraction. Jie et al. [121] studied the effect of an SBA−15-supported nickel metal
catalyst (Ni/SBA−15) on the HTL process and the yield of bio-oil. As shown in Figure 9a,
the liquefaction of rice straw at 280 ◦ C and 15 min undoubtedly yielded more bio-oil in the
range of 56.2–56.6 wt% of bio-oil at 10−15 wt% loading of Ni/SBA−15 in comparison to the
lower catalyst wt% or non-catalytic run. It was also observed that on a further increase of
the catalyst to 20 wt%, the bio-oil yield was reduced to 55.1 wt%, which was caused by the
enhanced cracking of macromolecules in rice straw to non-condensable gases [117]. Other
research also examined the effect of the wt% of heterogeneous catalysts on the yield of bio-
oil, as shown in Figure 9b, and found it to negatively affect the yield of bio-oil [37]. Thus,
the selection of the catalyst is an important task in the HTL process. Both homogenous
Energies 2021, 14, 4916 32 of 54

and heterogeneous catalysts were found effective in increasing the bio-oil yield and quality
when used in measured and experimental amounts. K2 CO3 is undoubtedly an excellent
choice. It helps to increase the bio-oil yield, reduce the char formation, and significantly
improve the quality of oil by increasing the carbon content and reducing oxygen, adding
to a higher HHV value.

Figure 9. Effect of heterogeneous catalyst concentration on the yield of bio-oil (a) catalyst with positive effect, (b) catalyst
with negative effect.
Energies 2021, 14, 4916 33 of 54

3.2. Effect of Solvents and Co-Solvents

The HTL process requires solvents that can effectively convert biomass into high-
energy density fuels of desired composition. In the last two decades, many solvents have
been utilized for the HTL process as described in Table 10.

Table 10. Studies focused on effect of various solvents for HTL.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Co-solvent mixture of ethanol–water is more
Highly efficient liquefaction of woody attractive for biomass liquefaction since ethanol is a
1 2010 biomass in hot-compressed [127]
renewable source of energy, which is easily produced
alcohol–water co-solvents. from fermentation of sugars.
Increased concentrations of ethanol in ethanol–water
mixture resulted in higher heavy oil yield and
Bio-oil from hydro-liquefaction of higher HHV.
2 2010 [128]
bagasse in supercritical ethanol.
Compound groups of phenolic, esters, and
aldehydes were mostly found in heavy oil.
Low ash content was found in heavy oil obtained
using ethanol–water mixture, making the heavy oil
Direct liquefaction of Dunaliella useful as a cleaner fuel, when compared to heavy oil
3 2012 tertiolecta for bio-oil in obtained using only pure water during liquefaction. [129]
sub/supercritical ethanol–water. Ethanol react with amides and/or acids to form ethyl
esters, and act as hydrogen-donor during
liquefaction process.
50 vol% water content enhanced solvolytic
liquefaction of pine.
Synergic effect of methanol and water
4 2013 Mixture of methanol and water promoted more [40]
on pine liquefaction.
decomposition of some plant tissue in pine when
compared to using purely methanol or water.
Heavy oil obtained after liquefaction in
Thermochemical liquefaction of rice ethanol–water mixture, showed mostly phenolic and
5 2013 husk for bio-oil production in mixed ester compounds to be present. [130]
solvent (ethanol–water). Presence of ethanol allowed high yields of heavy oil
with less severity in operation during liquefaction.
50:50 (v/v) of methanol–water mixture provided
highest heavy oil at 300 ◦ C and 15 min of
Cornstalk liquefaction in liquefaction process.
6 2014 [131]
methanol/water mixed solvents. Increasing water content led to cornstalk hydrolysis
and increasing methanol content led to
esterification reactions.
For liquefaction of wheat straw, the optimum
Hydrothermal liquefaction of wheat
7 2014 straw in hot compressed water and water–ethanol mixture ratio of 50:50 (v/v) was found [132]
to be effective in producing high yield of heavy oil
subcritical water-alcohol mixtures. and HHV at 300 ◦ C and 10 MPa.
Increasing trend of HHV was observed with increase
in ethanol concentrations, with 95 vol% ethanol to
give the highest HHV of heavy oil produced after
Hydrothermal liquefaction of bagasse liquefaction.
8 2015 Phenolic compounds and esters in heavy oil were
using ethanol and black liquor as [133]
solvents. observed to be decreasing with increase in water
content.
Alcohols, aromatics, and heterocyclic compounds in
heavy oil, were maximum when 50 vol% ethanol
was used for liquefaction.

Poplar liquefaction in water/methanol 70:30 (v/v) water–methanol mixtures resulted in

9 2015 complete degradation of cellulose and hemicellulose [134]
co-solvents. than for lignin.
Energies 2021, 14, 4916 34 of 54

Table 10. Cont.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Anisole–water mixture produced high yields of
heavy oil when compared to those when liquefied
Continuous hydrothermal liquefaction using toluene–water or n-heptane–water mixtures.
10 2016 of macroalgae in the presence of Viscosity of heavy oil when liquefaction was [135]
organic co-solvents. conducted with anisole–water mixture was much
higher when compared to those obtained by using
toluene–water and n-heptane–water mixtures.
Mixed ethanol/water solvent promoted the
permeation of the solvent into the lignocellulosic
Comparative study on lignocellulose structure and increased solubility of intermediates.
11 2018 liquefaction in water, ethanol, and Hot compressed water was found to promote [136]
water/ethanol mixture: role of ethanol
and water. hydrolysis of cellulose and hemicellulose, and
ethanol was found to accelerate degradation
of lignin.
50:50 (v/v) ethanol–water mixture efficiently
liquefied camphor tree sawdust at 280 ◦ C for 30 min,
Highly efficient conversion of camphor
with heavy oil yield of 61.5 wt%, higher conversion
12 2018 tree sawdust into bio-oil and biochar rate of 98.4%, and energy recovery rate of 94.5%. [137]
products by liquefaction in
ethanol–water co-solvent. Heavy oil produced using ethanol–water mixture
resulted in higher contents of esters and ketones and
lower amounts of nitrogenous compounds.
Optimum ethanol–water mixture of 75:25 (v/v)
provided the highest heavy oil yield at 220 ◦ C and
Liquefaction of sewage sludge in 30 min liquefaction conditions. The synergistic effect
13 2018 ethanol–water mixed solvents for [138]
bio-oil and biochar products. of ethanol–water mixture allowed liquefaction to be
conducted at mild operating conditions with
elevated yield and quality of heavy oil.
Methanol–water mixture promoted high content of
ester due to esterification. n-hexane–water promoted
Sub- and supercritical liquefaction of more aliphatic compounds to be formed, due to its
municipal wet sewage sludge to high solubility in n-hexane.
14 2018 [139]
produce bio-oil: effect of different Low-boiling point materials were found more in
organic–water mixed solvents. heavy oil obtained by methanol–water liquefaction.
Oxygen content in heavy oil reduced significantly in
n-hexane–water liquefaction.
Liquefaction of macroalgae at 300 ◦ C and 45 min,
using 75 vol% ethanol, provided the highest heavy
Effect of co-solvent and addition of oil yield of 46.75 wt%.
15 2019 catalyst (HZSM-5) on hydrothermal [140]
liquefaction of macroalgae. Catalyst HZSM-5 failed to provide high yield of
heavy oil; however, quality of heavy oil was
improved with high amounts of ester compounds.
Alkali-catalyzed liquefaction of Yield of heavy oil obtained by using ethanol–water
16 2020 pinewood sawdust in ethanol/water mixture for liquefaction can be compromised by [141]
co-solvents. using Na2 CO3 or NaOH as catalyst.
HTL of olive oil residue. At 300 ◦ C and 15 min, the use of methanol as solvent
Understanding the effect of using increased the oil yield from 30.8 wt% to 33.5 wt%,
17 2021 [85]
supercritical methanol as solvent on which further increased to 40.3 wt% in the presence
HTL of olive oil residue. of AlCl3 .
The highest HHV value of product was
Subcritical hydrothermal 42.02 MJ kg−1 at WSO–water ratio of 25:75.
co-liquefaction of process rejects at a The conversion was found to be highest at
waste paper-based paper mill with WSO–water ratio of 100:00.
18 2021 The percentage of alcohols, benzene, alkenyl, [142]
waste soybean oil.
phenols, and ester decreased with the increase of
Effect of solvent ratio of waste soybean
WSO–water ratio, whereas the percentage of acids
oil (WSO)–water was studied.
increased up to a WSO–water ratio of 50:50 on
further increase of the WSO–water ratio.
Energies 2021, 14, 4916 35 of 54

Among the HTL solvents, water is highly desirable for many liquefaction processes,
since it is the least expensive, is easily accessibility, and shows favorable chemical properties
that efficiently facilitate reactions. Water acts as reaction medium, solvent, and catalyst to
support various reactions during HTL. Water is considered one of the “green solvents”,
and with its physical and chemical properties at subcritical and supercritical states, it is
able to extract useful products from biomass during the liquefaction process [143]. The
critical point of water is 374 ◦ C and 22 MPa; above the supercritical point, water has no
phase boundaries, making it an excellent solvent. In this region, water has a high tendency
of diffusion and mass transfer owing to its low viscosity and high miscibility [3]. Below
the supercritical condition lies the subcritical zone of intermediate temperature which
supports primary hydrolysis and radical reactions through the formation of a pool of H+
and OH− ions [144]. However, both Ogi et al. [145] and Yuan et al. [146] have written about
obtaining highly viscous, tarry lumps of heavy oil when liquefaction is conducted with
only water as a solvent. Yuan et al. [146] further found that the efficiency of the liquefaction
of lignocellulosic biomass can be increased by using solvent mixtures rather than using
only one kind of solvent. As shown in Table 11, many different solvents have been studied
for the HTL of a varied range of biomasses, to understand the effect of solvents on the
product yield and composition.

Table 11. Major solvents and co-solvents used in the HTL process.

Operation Oil HHV C H O

Biomass Condition Co-Solvents Yield (MJ (wt.) (wt.) (wt.) Comments Ref.
(wt%) kg−1 )

50 vol% Bio-oil yield increased with solvent–water

38.35 29.66 - - - ratio, ranging from 0 to 50 vol%, and
Ethanol
T: 300 ◦ C decreased afterwards.
Rice straw Yields of residue were higher when [146]
R: 3 min
ethanol–water was used, when compared to
50 vol% 39.70 30.75 63.81 7.10 27.29 2-propanol–water mixture during the
2-Propanol
liquefaction process.

Water 18.51 30.77 72.57 6.88 20.55

20 vol% 22.80 37.17 79.25 8.69 12.06
1,4-dioxane Phenolic compounds are majorly present in
Rice straw T: 300 ◦ C liquefied products along with ester derivatives, [147]
R: 5 min 50 vol% 14.34 32.99 75.48 7.32 17.20
1,4-dioxane hydrocarbons, organic acids, and alcohols.
80 vol% 17.33 32.28 74.74 7.12 18.14
1,4-dioxane
1,4-dioxane 12.43 37.07 77.66 9.14 13.20
Water 39.13
50 wt% Liquefaction conducted with 50 wt% methanol
Ethanol 65.74 or ethanol in solvent–water mixture resulted in
T: 300 ◦C >95 wt% conversion of biomass and yield of
Pine wood Ethanol 25.92 - - - - [127]
R: 15 min bio-oil was >65 wt% at 300 ◦ C and a residence
50 wt% time of 15 min, compared to the runs using
Methanol 64.45
mono-solvents.
Methanol 23.54
50 vol% 42.44 21.4 - - -
Ethanol
70 vol% For 95 vol% ethanol and 5 vol% water mixture,
41.48 24.6 - - - there was a decrease in the amount of gas and
Ethanol
Sugarcane T: 330 ◦ C water products, resulting in a higher yield of
[128]
bagasse R: 40 min 90 vol% 45.03 24.7 - - - heavy oil.
Ethanol HHV increased with increasing ethanol
95 vol% concentrations, until 95 vol% ethanol.
48.24 27.1 56.5 6.8 34.7
Ethanol
Ethanol 39.55 24.2 - - -
Energies 2021, 14, 4916 36 of 54

Table 11. Cont.

Operation Oil HHV C H O

Biomass Condition Co-Solvents Yield (MJ (wt.) (wt.) (wt.) Comments Ref.
(wt%) kg−1 )
Water 13.16 25.03 60.55 6.93 30.24 Optimum ratio of 5:5 (v/v) ethanol–water
50 vol% mixture provided relatively high yield of oil
T: 260 ◦C 21.07 27.04 64.88 6.78 25.99
Rice husk Ethanol with low oxygen content. Ethanol provided [130]
R: 20 min decomposition of macromolecules such as
cellulose, hemicellulose, and lignin, at milder
Ethanol 18.44 27.56 63.63 7.46 26.23 operating conditions.

Methanol 24.25
20 vol% 40.02
Methanol More heavy oil was converted to char at
◦C
reaction temperatures above 300 ◦ C. Heavy oil
Pine wood T: 300 50 vol% - - - - yield increased until 15 min residence time [40]
R: 15 min 54.65
Methanol after which both gas and residue yields
80 vol% started increasing.
27.79
Methanol
Water 29.96
Water 25.8 20.5
25 vol% 22.2 25.5
Ethanol Water–ethanol mixture of 50:50 (v/v) used
Wheat T: 300 ◦C
50 vol% during liquefaction of wheat straw at 300 ◦ C
30.4 27.8 - - - [132]
straw R: 120 min Ethanol and 100 bar, effectively produced high heavy
oil yield of 30.4wt% with HHV of 27.8 MJ kg−1 .
75 vol% 32.7 28.5
Ethanol
Ethanol 43.2 28.2
Water 45.15
20 vol% 45.71
Methanol
40 vol% 48.07 Isometric methanol/water 50:50 (v/v) showed
Cornstalk T: 300 ◦ C Methanol - - - - the best synergistic effect on degradation [131]
R: 30 min of lignin.
50 vol% 52.40
Methanol
80 vol% 43.92
Methanol
Methanol 28.10
Water 28.8
20 vol% 36.2
Methanol
30 vol% More amounts of ketone, aldehyde, and
38.9 carboxylic acid were found in heavy oil
Methanol
T: 300 ◦C
Poplar - - - - liquefied with 70:30 (v/v) [134]
R: 15 min 40 vol% 37.3 water–methanol mixture.
Methanol Yield of esters decreased with an increase in
60 vol% water content in the solvent mixture.
31.8
Methanol
80 vol% 32.8
Methanol
Methanol 23.2
50 vol% glycerol decomposes the
lignocellulosic components to produce free
T: 260 ◦ C Glycerol– phenoxyl radicals that enable new compounds
Rice straw water 21.69 30.06 68.17 7.71 22.30 [148]
R: 60 min to be formed by
(1:1) (mL)
condensation/repolymerization reactions,
receding the residue formation.
10 wt% 7.23
n-heptane
Macroalgae T: 350 ◦ C 10 wt% - - - - Anisole led to an increase in heavy oil yield
[135]
R: 3 min 14.88 when compared to n-heptane and toluene.
Toluene
10 wt% 24.44
Anisole
Energies 2021, 14, 4916 37 of 54

Table 11. Cont.

Operation Oil HHV C H O

Biomass Condition Co-Solvents Yield (MJ (wt.) (wt.) (wt.) Comments Ref.
(wt%) kg−1 )
Camphor Conversion rate can be arranged from high to
tree T: 280 ◦ CR: 50:50 (v/v)
Water– 61.5 24.6 61.6 6.5 31.6 low efficiency of liquefaction as ethanol–water [135]
sawdust 30 min
(CTS) ethanol > only water > only ethanol.
Water 55.38 20.30 45.90 7.50 33.30
25 vol% 55.52 - - - -
Ethanol Heavy oil obtained by using ethanol–water
Sewage T: 220 ◦C mixture showed less content of long chain
50 vol% 34.87 25.10 54.50 7.90 26.40 [138]
sludge R: 30 min Ethanol carbon compounds (>C70), when compared to
using pure water as a solvent.
75 vol% 58.15 - - - -
Ethanol
Ethanol 66.41 27.00 58.40 8.00 24.10
34.14 73.94 10.55 9.34
50 vol% 39.4 ± ± ± ±
Methanol Effect of the reaction temperature on the yield
Sewage T: 340 ◦C 0.48 0.34 0.22 0.32 of heavy oil using different solvents showed [139]
sludge R: 20 min fewer changes, whereas the effect of the
36.45 73.08 10.75 7.65
50 vol% 38.6 ± ± ± ± residence time created significant changes to
n-hexane 0.38 0.23 0.12 0.26 heavy oil yield.
Water 13.93 - - -
25 vol% 23.22 - - - Using 75 vol% ethanol required high pressures
Ethanol of 20 MPa; hence, 50 vol% ethanol can be
T: 300 ◦ C 50 vol% considered as optimum alcohol–water mixture
Macroalgae 44.94 - 63.48 5.88 22.18 [140]
R: 45 min Ethanol that produced a similar yield of heavy oil with
reduced operating pressure required
75 vol% 46.75 - - - for liquefaction.
Ethanol
Ethanol 42.29 - - -
Heavy oil obtained by using ethanol–water
◦C 47.63 mixture contains high content of mild boiling
Pinewood T: 300 50 wt%
sawdust R: 30 min Ethanol ± 25.89 65.60 6.13 28.24 point materials (range of 343-538 ◦ C) than [141]
0.09 those obtained by using pure water for
liquefaction.

Some of the most common solvents used for the HTL process are acetone, methanol,
ethanol, 2-propanol, n-hexane, and n-heptane. Often these solvents are used as a co-solvent
with water. Several studies have focused on understanding and optimizing the ratio
of solvents with respect to water to improve product yield and quality. Ogi et al. [145]
suggested that adding organic solvents with water to biomass can improve the efficiency
of the continuous liquefaction process by making the heavy oil less viscous. They studied
solvents, such as acetone, propanol, butanol, methyl ethyl ketone, and EAC for liquefaction
and found that an acetone–water mixture produced heavy oil with less viscosity. In another
study, Ogi et al. [149] conducted hydrothermal liquefaction of oak wood chips with water
and 2-propanol at 275 ◦ C for 60 min. The water and 2-propanol ratio of 15:15 (v/v) mL
provided the highest yield of heavy oil (75.7 wt%). Heavy oil obtained using the water
and 2-propanol mixture resulted in decreased viscosity with no changes in the elemental
composition.
Yuan et al. [146] investigated the effects of an organic solvent–water mixture ratio on
HHV and the yield of heavy oil and solid residue at subcritical and supercritical conditions,
respectively. Liquefaction using either an ethanol–water or 2-propanol–water mixture
resulted in an increase in the heavy oil yield with an increase in the organic solvent–water
ratio from 0/10 (v/v) to 5/5 (v/v) and a decrease in heavy oil yield on further increase of
organic solvent. Yuan et al. [146] concluded that low-boiling point compounds, including
gaseous products, can be reduced by using an organic solvent–water mixture rather than
using purely one kind of solvent for liquefaction. Furthermore, a 2-propanol–water mixture
was found to provide both a higher yield of heavy oil and HHV than the ethanol–water
mixture for the liquefaction of rice straw.
Energies 2021, 14, 4916 38 of 54

Minami et al. [150] reported the benefits of using supercritical methanol (T = 239 ◦ C,
P = 8.1 MPa) as a co-solvent mixture with water for the liquefaction of beech wood.
Methanol, which has critical temperatures and pressures lower than those of water, tends
to lower the operating conditions of liquefaction. Methanol’s dielectric constant lowers
from 32 at ambient conditions to 7 when it reaches its critical point, which allows methanol
to dissolve many kinds of nonpolar organic substances and inorganic gases. It was also
observed that water played a significant role in the decomposition of lignin and hemi-
celluloses. Hence, a 10 vol% water with 90 vol% methanol proved to be effective for
decomposition and liquefaction. Zhu et al. [131] studied the effect of using water, methanol
and a methanol–water mixture as solvents for cornstalk liquefaction. It was found that
a 50/50 (v/v) ratio of a methanol–water mixture provided heavy oil with the highest
phenol content. In a similar study, Yan et al. [134] reported that methanol is effective
for the degradation of cellulose and hemicellulose, whereas better lignin degradation is
found when only water is used. Water contributed to the hydrolysis of cellulose and
hemicellulose components, and led to ketone formation through cyclization reactions and
methanol-facilitated esterification reactions [131,134].
Another solvent to consider is ethanol, which acts as an effective reaction substrate
and a hydrogen-donor solvent. It promotes heavy oil formation and reduces residual
generation [130]. Cheng et al. [127] carried out the liquefaction of white pine sawdust at
200–350 ◦ C and studied the effects of using pure solvents (methanol, ethanol and water) and
co-solvents (methanol–water and ethanol–water) on heavy oil yield and its composition.
A 50/50% (w/w) methanol–water mixture and 50/50% (w/w) ethanol–water mixture
produced same yields of heavy oil and it was higher than that obtained during individual
solvent run. Ethanol has been considered a better solvent than methanol in terms of the
conversion rate of biomass, as ethanol reduces the surface tension of liquefied products
and improves the diffusion of solvents in a lignin matrix. The FTIR results of heavy oil
showed that ethanol plays a major role in lignin decomposition, whereas water contributed
to the complete decomposition of cellulose and hemicellulose components of the biomass.
Phenolic compounds were detected to be greater in heavy oil produced from liquefaction
conducted with pure ethanol when compared to those obtained from an ethanol–water
mixture [127].
Feng et al. [136] showed that the liquefaction process can be ranked from high to
low efficiency based on the type of solvent media used and is arranged as: 50/50 (v/v)
water–ethanol mixture > pure water > pure ethanol, irrespective of the type of biomass
feedstock. A 50/50 (v/v) water–ethanol mixture showed a high synergistic effect during
the liquefaction of lignocellulosic biomass conducted at 300 ◦ C for a retention time of
15 min. The role of water was primarily to hydrolyze cellulose and hemicellulose, whereas
ethanol allowed lignin degradation, preventing further repolymerization reactions of
intermediate materials. Since ethanol is primarily responsible for lignin degradation, using
ethanol as the sole solvent can produce high quality heavy oil and is a better solvent
medium for the liquefaction of high lignin-content biomass. Hence, for the liquefaction
of biomass composed of all three major components (cellulose, hemicellulose and lignin),
the ethanol–water mixture is more reliable, reducing the need to select a distinct type of
biomass [136].
Li et al. [147] performed liquefaction of rice straw with a 1,4-dioxane–water mixture.
The group studied the impact of a co-solvent mixture ratio on both the yield and quality of
heavy oil. With the calculated values of critical temperature and pressure for a 50 vol% of
1,4-dioxane, it was noted that using a 1,4-dioxane–water mixture at a reaction temperature
of 340 ◦ C provided supercritical conditions which allowed chemical reactions to occur in
a single fluid phase system [147]. The single fluid phase system provided the advantage
of attaining higher concentrations of reactants, since there are no existing interphase
mass transport processes that can hinder reaction rates [151]. The maximum oil yield of
22.80 wt% with the highest HHV (37.17 MJ kg−1 ) was obtained for a 20 vol% of a 1,4-
dioxane–water mixture. Deoxygenation and decarboxylation reactions were occurring
Energies 2021, 14, 4916 39 of 54

during the liquefaction of rice straw with a 1,4-dioxane water mixture, leading to an
oxygen transfer from a heavy oil fraction to the aqueous phase, thus reducing the oxygen
content of heavy oil. In regard to the decomposition mechanisms of lignin, cellulose, and
hemicellulose, water acts as a nucleophile and reacts with some of the active centers in proto-
lignin whereas 1,4-dioxane solubilizes cellulose and hemicellulose components and carries
reactants to proto-lignin and the resulting lignin fragments to the solution [147,152,153].
Li et al. [147] also reported that nucleophilic and hydrolytic functions of water weakened
with a higher content of 1,4-dioxane (80 and 100 vol%) in a co-solvent mixture, thereby
reducing the phenolic, acidic, hydrocarbon, and ester derivatives in heavy oil. Although
50 vol% 1,4-dioxane produced a high heavy oil yield, a reduced 1,4-dioxane content could
potentially affect the quality of heavy oil in terms of the acid content. However, not many
researchers have focused on the use of 1,4-dioxane due to its carcinogenic nature [148].
The use of other organic solvents is also reported for feedstocks other than pure
lignocellulosic material, such as microalgae and sewage sludge. He et al. [135] reported
the liquefaction of microalgae in the presence of individual 10 wt% anisole, toluene, and
n-heptane with water. It was observed that the anisole–water mixture led to a higher
heavy oil yield compared to the yields obtained from using the toluene–water or n-heptane–
water mixtures. One possible reason may be the increased solubility of anisole in water at
temperatures above 275 ◦ C. Water alone provides limited solubility of organics, whereas in
the presence of anisole the solubility of organics increases. Moreover, the anisole–water
mixture inhibits the polymerization of reactive intermediates. However, heavy oil obtained
from using the anisole–water co-solvent mixture showed higher viscosity than the heavy
oil obtained with the other solvent–water mixtures. Li et al. [139] reported the effect of
using a methanol–water mixture and an n-hexane–water mixture for the liquefaction of wet
sewage sludge (WSS). Both the solid residue and gaseous products obtained were less when
using the n-hexane–water co-solvent mixture when compared to using the methanol–water
mixture. Interestingly it was observed that only at higher temperatures and pressures
n-hexane showed better efficacy in extracting high yields of heavy oil, whereas methanol
was able to produce similar yields at comparatively lower operating temperatures. In
terms of calorific values obtained from heavy oil, the order of solvents was n-hexane–water
> methanol–water > pure water. Overall, the n-hexane–water mixture provided a higher
heavy oil yield with a low oxygen content, high HHV and greater thermal stability, but at
the cost of higher operating temperatures and pressures.
Therefore, the synergistic effect of using an organic solvent–water mixture improves
the liquefaction process of biomass. The water promoted the decomposition of lignin, cellu-
lose, and hemicellulose, and the hydrogen donor organic solvents showed greater affinity
towards lignin decomposition, along with the reduction of intermediate polymerization
and residual formation. The oil obtained showed reduced oxygen content and high carbon
content and HHV value.

3.3. Effect of Extraction Solvent on Products

The procedure implemented to separate and extract the products from HTL of biomass
plays a very important role. However, it is unclear how much the type of solvent used
during heavy oil extraction affects the yield and composition. Tables 12 and 13 sum-
marize some studies about the effect of different extraction solvents on the bio-oil yield
and composition.
Many studies on the effect of extractive solvent are available for the HTL of microalgae.
Valdez et al. [154] studied the effect of solvents on the yields and compositions of products
recovered from the HTL of marine microalga Nannochloropsis sp. Polar solvents, such as
methoxy cyclopentane, chloroform, and DCM, and non-polar solvents, such as hexadecane,
decane, hexane, and cyclohexane were individually utilized for the extraction procedure.
Non-polar solvents have been shown to increase the yield of bio-oil and aqueous phase oil
when compared to yields from polar solvents [154]. The heavy oil extracted from using
either polar or non-polar solvents was enriched with C and H content and had reduced
Energies 2021, 14, 4916 40 of 54

the N content compared to the original feedstock composition. Heavy oil extracted with
the polar solvent showed the highest carbon content. DCM showed the lowest heavy oil
yield compared to the rest of the solvents [154]. The GC–MS analysis results showed heavy
oil extracted using polar solvents had produced higher amounts of aliphatic compounds,
whereas the heavy oil extracted using chlorinated solvents (chloroform and DCM) had
high amounts of light ends and fatty acid derivatives. In a similar study, Yan et al. [155]
examined the effect of 10 organic solvents with different polarities: isopropanol, EAC, DCM,
DEE, dichloroethane, benzene, carbon disulfide, cyclohexane, n-hexane, and petroleum
ether. Yan et al. [155] reported that solvents with higher polarity produced higher yields of
heavy oil, a finding that contradicted Valdez [154].

Table 12. Studies on effect of extractive solvent in HTL operations.

S. No Year Description/Objective Results/Observations/Major Findings Ref.

Non-polar solvents have been observed to provide high
Characterization of product fractions
gravimetric yields of heavy oil, but these oils contain low
from hydrothermal liquefaction of
1 2011 carbon content and show less energy density. [154]
Nannochloropsis sp. and the influence
Polar solvents have shown low yields of heavy oil, but these
of solvents.
oils contain high fatty acid content.
Selective extraction of bio-oil from Heavy oil was extracted using 9 organic solvents with
hydrothermal liquefaction of Salix
different polarities in the order of high to low
2 2014 psammophila by organic solvents with [32]
efficiency—THF > toluene > EAC > acetone > ether > DCM >
different polarities through multistep
extraction separation. methanol > petroleum ether > n-hexane.

Highest yield of heavy oil was obtained by using acetone as

an extraction solvent.
Analysis of physicochemical Heavy oil extracted by hexane was suggested to be the best
3 2016 properties of bio-oil from HTL of [69]
performing fuel in terms of quality since the heavy oil
blackcurrant pomace. showed low carbon residue, volatility close to that of diesel
and HHV close to those fuels used in marine applications.
Polarity and molecular structure of extraction solvent greatly
Composition of the bio-oil from the affects the yield and composition of heavy oil.
4 2016 HTL of duckweed and the influence of Heavy oil extracted by using polar solvents showed high [155]
the extraction solvents. yields, high C and H content, and high energy density when
compared to those extracted by using non-polar solvents.
110th anniversary: influence of Solvent type for extraction was confirmed to affect the yield
solvents on bio-crude from of heavy oil recovered from two different HTL processes.
5 2019 hydrothermal liquefaction of soybean [68]
oil, soy protein, cellulose, xylose, and Polarity of solvent cannot be the sole determinant of
lignin, and their quinary mixture. evaluating its performance during the extraction process.

Yang et al. [156] performed sequential selective extraction and separation of bio-oil
obtained from liquefaction of Salix psammophila using nine different organic solvents
with different polarities. The order of solvents for bio-oil extraction yield from high to low:
THF > toluene > EAC > acetone > ether > methylene chloride > methanol > petroleum
ether > n-hexane. It also investigated the effect of various solvents on extracting medium-
molecular compounds (oligomers) from high-valued low-molecular weight chemicals (e.g.,
2-cyclopenten-1-one, 2-methyl-, phenol, 2-methoxy-, phenol and 2,6-dimethoxy-, phenol)
that can be used directly in industrial applications or to separate oil fractions. The yield of
extracted heavy oil varied differently and not linearly with the polarity of solvents [156].
High amounts of ketones, phenolics, and alkoxy phenolics were extracted by highly polar
solvents, such as THF, EAC, and acetone. For better analysis of the components of heavy
oil fractions, a suggestion was made to extract several fractions of heavy oil using different
solvents in a proper sequence of their polarities [156]. A multistep extraction method
conducted in this work involves using three organic solvents arranged from high to low
polarities (THF, EAC, and n-hexane), where the solvent with lowest polarity was used in
the final step to extract light fractions.
Anouti et al. [69] focused on the impact of solvent types on heavy oil quality extracted
after the HTL of blackcurrant pomace as a biomass feedstock. EAC, hexane, acetone, and
Energies 2021, 14, 4916 41 of 54

isopropyl alcohol were the selected solvents used for extraction. The organic solvents
recover heavy oil from solid residue and the remaining solvent is evaporated. The evapora-
tion step resulted in loss of the light volatile fractions with the solvent, thus affecting the
composition of heavy oil. Acetone extracted the highest yield of heavy oil compared to the
other solvents, which indicates that acetone, which has the highest polarity, was able to
produce high yields of heavy oil. However, hexane was found to be an effective solvent
to produce high quality heavy oil compared to the other solvents. Thus, the polarity of a
solvent plays an important role in bio-oil extraction [69,155].
Along with the extraction solvent, the separation technique also affects the properties
of bio-oil. Yang et al. [157] conducted HTL on three different feedstocks (Chlorella sp.
(C. sp.), spent coffee grounds (SCG), 50/50 Chlorella sp./spent coffee grounds (C. sp./SCG))
and investigated the effect of different separation techniques and types of solvent on the
yield and physicochemical (i.e., chemical composition and dynamic viscosity) properties of
heavy oil. Yang [157] suggested using solvents with a wide range of dielectric constants, as
a solvent’s polarity is closely linked to its dielectric properties. Solvent extraction, Soxhlet
filtration, and microwave-assisted extraction methods were used as separation techniques
to recover heavy oil. From the results obtained after the extraction procedures, it was
found that DCM and THF extracted high yields of heavy oil and hexane gave the lowest
yield. Interestingly, acetone, which has the highest dielectric constant (21.0) and a high
polarity value (4.3), produced a heavy oil yield lower than that obtained by DCM and
THF [156,157]. The heavy oil yield was independent of the separation techniques, but
filtration was suggested to be the best method to extract heavy oil based on operation costs
incurred during the separation process. Furthermore, a change in separation technique did
not affect the yield and physical properties of the heavy oil extracted with different solvents,
but the type of solvent and feedstock affected the viscosity of the extracted heavy oil [157].
Lu et al. [68] experimented with different solvents (DCM, acetone, MTBE) to under-
stand their effect on the yield and elemental composition of heavy oil recovered from
HTL processes on different feedstocks (soybean oil, soy protein, cellulose, xylose, lignin,
and quinary mixture). Heavy oil yields derived from soybean oil and soy protein did
not vary with different solvents, though acetone was found to produce a high yield of
heavy oil during the HTL of feedstocks that were high in cellulose, xylose, and lignin. Lu
et al. [68] observed that the yield of heavy oil from the HTL of feedstocks that are rich in
saccharides and lignin is greatly affected by what type of solvent is used for extraction.
Acetone exhibited the highest yield of heavy oil extracted, whereas DCM produced the
lowest yields of heavy oil, which indicates that even solvents such as acetone and DCM
with similar polarities produce varying yields of bio-oil. Hence, the polarity of a solvent
cannot be the sole determinant in evaluating an extraction solvent’s performance. There
seems to a strong agreement from Valdez et al. [154], Xu et al. [158], Watson et al. [159], and
Lu et al. [68] that solvent type plays a critical role in the yield and chemical composition of
heavy oil extracted from HTL products.

Table 13. Effect of extraction solvents on separation of products during HTL.

HHV
Operation Extraction Oil C H O
Biomass (MJ Comments Ref.
Conditions Solvent (wt%) (wt%) (wt%) (wt%)
kg−1 )
Hexadecane 38.66 - - -
Decane 39.39 - 68.80 9.37
Hexane 31.79 - 70.45 9.80 DCM and chloroform were found
Marine T: 350 ◦ C Cyclohexane 33.68 - 64.87 9.76 - more effective in extraction of [154]
algae R: 60 min light ends and fatty acids
Methoxycyclopentane 31.91 - 72.27 9.70 derivatives.
Chloroform 34.75 - 73.68 9.85
DCM 30.14 - 75.76 10.57
Energies 2021, 14, 4916 42 of 54

Table 13. Cont.

Operation Extraction HHV C H O

Biomass Oil (MJ Comments
Conditions Solvent (wt%) (wt%) (wt%) Ref.
(wt%) kg−1 )
Petroleum ether 12.95 -
n-hexane 8.27 - Ketones and phenolic compounds
Toluene 38.31 - were easily extracted with high
polarity solvents such as THF,
Ether 28.10 - EAC, acetone, and methanol.
Willow T: 300 ◦ C - - - Multistep-extraction procedure [156]
branches R: 30 min DCM 26.78 -
provided efficient separation of
THF 45.34 - bio-oil components and
EAC 30.55 - sequential analysis of
components.
Acetone 30.00 -
Methanol 23.32 -
EAC 28 ± 3 33.4 75 ± 1
◦C Hexane 17 ± 3 38.4 80 ± 1 Heavy oil extracted using hexane
Blackcurrant T: 300 - - resulted in having high quality [69]
pomace R: 60 min Acetone 32 ± 3 35.0 74 ± 1 with high C-content and HHV.
Isopropyl alcohol 29 ± 3 34.6 73 ± 1
Isopropanol 26 ± 1 34 ± 2 70 ± 0.7 9 ± 0.5 14 ± 0.7 Highest yield of heavy oil was
produced by using isopropanol as
Dichloroethane 19 ± 1 36 ± 2 74 ± 0.7 9 ± 0.4 10 ± 0.5
the extraction solvent.
DCM 24 ± 1 37 ± 2 76 ± 0.8 9 ± 0.4 8 ± 0.4 Isopropanol was found to be
miscible with water, and hence
EAC 20 ± 1 37 ± 2 76 ± 0.8 9 ± 0.4 8 ± 0.4 only one phase was separated
Duckweed T: 350 ◦ C DEE 17 ± 0.8 37 ± 2 76 ± 0.8 9 ± 0.5 8 ± 0.4 since water-soluble products did [155]
R: 30 min not create a separate phase.
Benzene 18 ± 0.9 38 ± 2 77 ± 0.8 9 ± 0.5 7 ± 0.4 Carbon disulfide being a
Carbon disulfide 17 ± 0.9 38 ± 2 76 ± 0.8 9 ± 0.5 7 ± 0.3 non-polar solvent was able to
extract high yields of heavy oil
n-Hexane 3 ± 0.2 40 ± 2 78 ± 0.8 10 ± 0.5 6 ± 0.3 when compared to those
Cyclohexane 9 ± 0.4 39 ± 2 78 ± 0.8 10 ± 0.5 7 ± 0.3 extracted by n-hexane,
cyclohexane, and petroleum ether.
Petroleum ether 4 ± 0.2 40 ± 2 78 ± 0.8 10 ± 0.5 6 ± 0.3
T: 400 ◦ C
DCM 29.5 ± 2.1 - Heavy oil yield increased when
R: 60 min
DCM was used as an extraction
Microalgae - - - solvent. HHV of heavy oil [160]
T: 400 ◦ C extracted by either DCM or MTBE
MTBE 24.5 ± 2.3 -
R: 60 min did not have a major difference.

Acetone 28.22 35.5 70.0 ± 1.8 10.5 ± 0.3 17.8 Acetone-extracted heavy oil
shows high N and S content from
liquefaction of high-carbohydrate
Chlorella sp. T: 260 ◦ C and high-ash content biomass. [159]
R: 60 min DCM 48.70 39.5 74.6 ± 0.2 11.6 ± 0.1 13.1
DCM and toluene-extracted
heavy oil showed high N and S
content from liquefaction of
Toluene 28.60 37.4 72.0 ± 0.8 11.2 ± 0.1 16.0
high-protein content biomass.

Hexane 15.2 ± 1.0 DCM, THF, and acetone were

effective solvents for extraction,
giving higher yields of heavy oil
when compared to hexane.
Spent coffee Acetone 32.3 ± 1.0
T: 290 ◦ C Hexane was an effective solvent
grounds during Soxhlet separation method [157]
R: 10 min
(SCG) and was able to recover more heavy
DCM 32.8 ± 1.2 oil when compared to the rest three
solvents. Yield of heavy oil
extracted by filtration is mentioned
THF 38.1 ± 2.2 here since filtration was the most
efficient separation method.
DCM 4.40 32.3 72.8 6.8 20.1 Individual feedstock containing
Cellulose cellulose, xylose, and lignin in
Acetone 10.92 30.2 70.8 6.3 25.3
high amounts, showed that the
MTBE 5.71 32.8 71.6 7.6 21.4 heavy oil extracted did not
DCM 6.36 31.9 73.2 6.5 20.2 depend on solvent type.
T: 350 ◦C
Xylose It is difficult to achieve the high [68]
R: 30 min Acetone 10.52 30.2 70.1 6.3 23.4 yields and high HHV from heavy
MTBE 8.15 32.4 71.6 7.3 21.8 oil extracted by a certain
kind of solvent.
DCM 1.22 32.1 70.1 7.5 22.1
Lignin
Acetone 14.35 17.9 46.8 5.4 46.3
MTBE 2.77 19.9 51.7 5.2 41.2

EAC: ethyl acetate, DCM: dichloromethane, MTBE: methyl tert-butyl ether, THF: tetrahydrofuran, IPA: isopropyl alcohol, DEE: diethyl ether.
Energies 2021, 14, 4916 43 of 54

4. HTL Products and Applications

4.1. Bio-Oil
Bio-crude/bio-oil or heavy oil produced from the HTL process is a brown to dark
brown, highly viscous liquid with a high carbon, low oxygen content and an overall
high HHV value ranging from 25 to 40 MJ kg−1 . Bio-oil is a mixture of complex chemi-
cal compounds, which includes ketones, aldehydes, phenolics, phenyl derivatives, fatty
acids, esters, fatty acid alky esters, alcohols, polyols, unsaturated hydrocarbons, and sat-
urated hydrocarbons and some fraction of nitrogenous compounds such as amine and
amides [24,161]. The biomass degradation, route of conversion, intermediate formation,
and interaction, and the rate kinetics are decided with respect to the process parameters
and solvent type as discussed in Sections 2 and 3. All these factors affect the bio-oil
yield, chemical composition, and physical properties, such as viscosity and total acid
number value.
In the modern economy, more and more attention has been focused on sustainable
fuels and chemicals. Bio-oil has a huge potential to meet these requirements. When
compared with conventional fuels such as gasoline and diesel, bio-oil has a high total
acid number (TAN), viscosity and water content [69,79,162]. Taghipour et al. [163] has
summarized the properties of crude bio-oil obtained from various sources. Because crude
bio-oil has a higher TAN number, it is very corrosive in nature due to which it is difficult
to store and operate on crude bio-oil. Its increased viscosity also increases the challenges
associated with transporting bio-oil. Its high-water content reduces its total combustion
energy. Without definite properties, it becomes increasingly challenging to use bio-oil on
existing boilers and/or gasifiers. Hence, to substitute conventional fuels with bio-oil, one
possible application in this field is bio-oil upgrading and separation to obtain different
classes of fuels from complex crude bio-oil mixtures.
Taghipour et al. [163] reviewed literature on the fractional distillation of crude bio-oil
and presented a detailed description of the potential application of distillates of bio-oil.
They also discussed about the effect of distillation on chemical composition, heating value,
viscosity, density, water content, miscibility, storage, and stability. Pedersen et al. [164]
performed fractional distillation of bio-crude obtained from HTL and found six distil-
late fractions and distillate residue; the lighter distillate fraction was comprised of light
oxygenates, which can be a potential option to produce useful chemicals. A mixture of
ketones was obtained, which can act as a precursor for liquid transport fuels. The bio-oil
can also be used to produce other higher value fuels such as jet fuel, gasoline, diesel,
and hydrogen-rich gas. Tzanetis et al. [165] developed a method to produce jet fuel from
bio-crude. First, crude bio-oil was upgraded through hydrotreatment to reduce the oxygen
content, producing hydrogen-rich gas, a mixture of jet fuel, gasoline, diesel, and heavy
oil, along with a waste aqueous stream. Next, fractional distillation was performed to
obtain individual fractions. The H2 -rich gas obtained in first step was used recirculated
in the upgrading process. Apart from developing useful fuels, bio-oil can also be used to
synthesis many other industrial chemicals [166–169].

4.2. Aqueous Phase

The aqueous phase is formed as a secondary product in a batch process and as a side
stream of process water in a continuous operation. With an advancement in the field of
HTL and the shift of focus from batch to the development of a continuous operation, there
is an increasing need to advance our understanding of the aqueous phase to make the
overall process more viable. Approximately 25% to 50% of the carbon present in biomass
can end up in an aqueous phase [170]. This also highlights the need to develop techniques
and methodology to understand the properties and composition of the aqueous phase.
The aqueous phase mainly comprises low molecular-weight organic acids and polyols,
a moderate fraction of phenolic compounds and ketones, and a small amount of sugar. The
major fraction acid accounts for 40%–50% of the weight of the aqueous phase and is mainly
a mixture of acetic acid, lactic acid, glycolic acid, propionic acid, formic acid, butanoic
Energies 2021, 14, 4916 44 of 54

acid, pentenoic acid, and butenedioic acid. The alcohols and polyols mainly consist of
methanol, glycol, ethylene glycol, propylene glycol, catechol, glycerol, D-glucitol, xylitol,
and ribitol [27,170].
The large quantity of the aqueous phase produced in HTL raises a concern about the
economic efficiency of the process and its use. Using the aqueous phase for recirculation as
a solvent in a continuous operation and using the aqueous phase for the next HTL run in a
batch cycle can significantly help to utilize it. The use of aqueous phase for recirculation
also has potential benefits for the yield and quality enhancement of bio-oil and hydrochar.
It reduces the requirement for process water treatment and limits the consumption of
fresh water. When Zhu et al. [23] recirculated the aqueous phase during the HTL of barley
straw, the result was an increase in the yield of bio-oil from 34.9 wt% to 38.4 wt% after
three runs. This increase was associated with the presence of organics in the aqueous
phase, which accelerated the overall decomposition of the biomass. Biller et al. [171] also
investigated the effect of aqueous phase recirculation on the HTL of dry distillers’ grain in
the presence of K2 CO3 and observed an increase in bio-oil yield from 44.3% to 60% after
the first recirculation. The yield of solid residue also increased from 1.2% to 14% after the
seventh recirculation run.
Many studies suggested other possible options such as the catalytic cracking of the
aqueous phase product to obtain valuable chemicals such as olefins and aromatic hydro-
carbons such as benzene, toluene, and xylene. Miyata et al. [172] developed a method to
separate the light water-soluble fraction (by freeze drying) and heavy water-soluble fraction
(by water removal) and conducted catalytic cracking on separated fractions, producing an
olefins + BTX yield of 49% and 14%, respectively.
Another less researched application for the aqueous phase is catalytic hydrothermal
gasification to produce fuel gas, which mainly consists of CO2 , CH4 , and H2 [10,173]. The
idea of a catalytic supercritical hydrothermal gasification of the aqueous phase from the
HTL of microalgae biomass to produce H2 -rich gas can also be applied for the aqueous
phase generated during the HTL of lignocellulosic biomass [174]. Even though there is a lot
of potential, more knowledge is needed before we can aptly implement the aqueous phase.

4.3. Char
During hydrothermal liquefaction, the main product obtained is bio-oil, whereas
in hydrothermal carbonization the main product is char. The solid by-product obtained
using HTL is known as either solid residue, residue, char, biochar, or hydrochar. The yield
of char depends greatly on the type and composition of biomass. The yield may range
anywhere from ~5–60 wt% [27,73,82,96,114]. Biomass with a high lignin content tends to
produce more char than one with more cellulose and hemicellulose. Demirbas et al. [175]
investigated the effect of lignin content on oil and char yield and found that biomass with
a high lignin content in the range of 41–48 wt% produced a solid residue of 40–50 wt%,
whereas the one with a low lignin content of about 14–27 wt% (cellulose: 45–50 wt%)
provided a solid residue yield of 21–26 wt%.
The yield of char and its chemical composition significantly depend on the process
parameters, such as temperature, pressure, retention time, biomass-to-solvent ratio, and
type and concentration of catalyst. The char contains a high C and H, low O, and high
HHV value compared with biomass. For the solid residue obtained from lignocellulosic
biomass, the C wt% ranges from 55–78 wt%, the H wt% ranges from 4–6 wt% and the
oxygen content ranges from 15–35 wt% [176,177]. It is also observed that the percentage of
nitrogen is more in solid residue when compared to biomass [7,178].
The char from the HTL has very promising qualities, which are encouraging for its
application in the energy sector, soil enhancement and as an adsorbent. The char tends to
have a high hydrophobicity; it allows easy handling and storage since it poses a higher
resistance to humidity [176]. The char can have both a positive and negative effect on soil
fertility. It is required to go through some pre-treatment in order to reduce its negative
effect on plant growth [179]. It can have varied mineral and organic contents based on
Energies 2021, 14, 4916 45 of 54

biomass sources. These contents can include a high C:N ratio and low mineral-N or low
C:N ratio and high mineral-N, as well as many other minerals. It is important to investigate
the char ratio with fertilizer so that a proper intake can take place in the plant for growth
and so that no additional N is left behind to emit toxic chemicals [179–181].
The char obtained from the HTL process has a high calorific value and can be used
for energy applications such as direct combustion or co-combustion with coal or it can
be used to prepare energy storage materials such as bio-batteries, fuel cells, and bio-
capacitors [79,120,182,183]. The hydrochar obtained from HTL shows a significant reduc-
tion in ash content when compared to char from other processes and biomass. The inorganic
minerals such as Ca, Si, Na, K, Mg, P, Fe, and Mn are mostly present in hemicellulose
and are leached out in a hot compressed solvent. This makes hydrochar a cleaner fuel by
eradicating the negatives that cause fouling, corrosion, scaling, and slagging, and promote
toxicity in water and air during combustion [184,185].
The char can also be used as an adsorbent to remove pollutants such as heavy metals
and organic materials from flue gas, water, and wastewater. Liu et al. [178] studied the
characteristic properties of char obtained from the HTL of pinewood and rice husks and
experimented to determine if they could be used to remove lead from an aqueous solution.
It was observed that more irregular surfaces and oxygen-containing functional groups
were developed on the char. The maximum lead adsorption capacity was 2.40 to 4.25 mg/g
for rice husks and pinewood char, respectively. In brief, char has high energy density and
better qualities than biomass for various applications, but to use it with present technology,
more quality work is needed to make sure it meets environmental standards and to better
understand the life cycle assessment.

4.4. Gases
Gas products also one of the by-products obtained in the HTL process. Due to the
poor gas composition in the process, as shown in Table 14, and because bio-oil is considered
more important, gas is either not analyzed or included with other products [27,98,186].
In general, the gas fraction accounts for 5–15 wt% (T: 250–375 ◦ C) of the total product
distribution from HTL [70,81]. The yield of gases is greatly enhanced with temperatures
near and above the critical point of water. Alba et al. [73] investigated the liquefaction
of microalgae over a temperature range of 175–450 ◦ C and observed that the yield of
gas was negligible near 200 ◦ C and 15% at 300 ◦ C, which increased significantly as the
temperature crossed 375 ◦ C (24%) and reached a value of 47.4% at 450 ◦ C while all other
product fractions kept decreasing. Many other studies observed similar trends for the gas
yield near the supercritical condition [24,78,97]. Furthermore, an increase in retention time
at subcritical and supercritical temperatures increased the gas yield. One possible reason
for the increase in the gas fraction is the increased cracking of oil and char. Yang et al. [97]
and Brand et al. [98] observed that a fraction of CO2 dominates in gas up to 300–325 ◦ C but
on a further increase in temperature, the CO starts to dominate, followed by CO2 . Other
compounds observed in gas were H2 , short chain alkenes, and alkanes (CH4 , C2 H6 , C3 H8 ,
C2 H4 ), but the amounts are negligible. Isa et al. [78] studied the conversion of miscanthus
in anhydrous state and in the presence of supercritical water media and observed an
increase in the Ci (i = 1–4) yield from 1.9 wt% (anhydrous) to 2.44 wt% (supercritical water).
A similar increase was observed in the total yield of H2 , CO, and CO2 from 24.3 wt%
(anhydrous) to 30.3 wt% (supercritical water). It was also observed that the increased water
content in the reactor decreased the CO fraction from 3.9 wt% (anhydrous) to 0.3 wt%
(supercritical water).
Energies 2021, 14, 4916 46 of 54

Table 14. Various gas compositions obtained from the HTL process.

Biomass Gas Yield (wt%) Composition Comments Ref.

CO2 dominates near 300 ◦ C,and CO starts to
CO2 , CO, C2 H4 , dominate over 325 ◦ C.
Birch wood 1–12 [97]
C2 H6 , C3 H8 Fraction of methane increases significantly
above 350 ◦ C.
Wet and Dry distiller’s CO2 , H2 , N2 , CO, CH4 ,
~15% 96% of the gas was CO2 and 1.6% H2 . [59]
grains and solubles light alkanes and alkenes
General trend of gas fraction CO > CO2 >
C2 H4 > CH4 > C2 H6 .
CO2 , H2 , CO, CH4 , C2 H6 ,
Red pine sawdust 0.2–8.7 (mol%) The amount of H2 and C3 –C6 was negligible. [98]
C2 H4 , C3 –C6 (negligible)
At 400 ◦ C, compounds like C2 –C6 were
also present.
CO2 , CO, CH4 , H2 ,
CO diminished with increase in water ratio in
Miscanthus ~20–37 C2 H4 , C2 H6 , C3 H6 , [78]
the reactor.
C3 H8 , C4 H10
Corn straw 16.5 H2 (1.9%), CO (6.2%), CH4 (0.9%), CO2 (90.8%), C2 H6 (0.2%), C2 H8 (0.1%)
Peanut straw 19.9 H2 (2.7%), CO (4.2%), CH4 (1.1%), CO2 (91.6%), C2 H6 (0.1%), C2 H8 (0.2%) [23]
Soybean straw 19.7 H2 (3.1%), CO (5.5%), CH4 (0.6%), CO2 (90.6%), C2 H6 (0.1%), C2 H8 (0.1%)
Rice straw 22.9 H2 (2.2%), CO (6.2%), CH4 (1.1%), CO2 (90.2%), C2 H6 (0.1%), C2 H8 (2.2%)

CO2 and CO are mainly formed by the decomposition of oxygen-containing groups in

the lignocellulosic biomass through decarboxylation and decarbonylation reactions. CH4 is
formed via the decomposition of a methoxy group whereas other short-chain hydrocarbons
(C2 –C3 ) are formed during the cracking of long-chain hydrocarbons and aromatics [98].
Some researchers did focus on the quantification and composition analysis of the gas
phase on a lab scale model. However, only limited data are available on the gas phase
applicability and potential for a large-scale operation. Future works can aim to clarify
how gas yield and composition vary when operations are scaled, and how to separate and
increase light hydrocarbon fractions from obtained gases.

5. Conclusions
Currently, biomass-derived fuels seem to provide a viable solution to the search for
alternative and renewable fuel sources. HTL is one of the many available approaches to
convert biomass into biofuels.
• A suitable range of temperatures for the HTL of agricultural and forest-based residues
is 275–325 ◦ C and the choice of a final temperature strongly varies with the feedstock
composition. A lower final temperature results in an incomplete conversion, whereas
a temperature above 350 ◦ C promotes carbonization and cracking, leading to an
increased char and gas yield.
• Water enhances the decomposition of cellulose, hemicellulose, and to some extent,
lignin. The organic solvents help in degradation of lignin. The synergistic effect of
using an organic solvent–water mixture during HTL improves the overall liquefac-
tion process.
• In the presence of extraction solvents, many macromolecular oligomers are dissolved,
leading to the formation of new compounds and high-value chemicals.
• The catalysts are important to trigger earlier and faster biomass degradation by
activating the kinetics of primary reactions, hindering secondary reactions, such as
repolymerization and cracking, and reducing dependency on other parameters, such
as pressure, temperature, and retention time.
Energies 2021, 14, 4916 47 of 54

• Undoubtedly, alkali metals are the most effective at easing the degradation of biomass
because they disrupt the physical barrier in the biomass. More generally, K2 CO3 is a
first-rate choice for a catalyst.
• Pressure is important to maintain a single-phase liquid slurry of the feed material so
that the reaction can proceed smoothly. In the subcritical temperature range, pressure
has some effect on the bio-oil yield, whereas at supercritical conditions, even a pressure
of 30–40 MPa is inadequate to affect hydrolysis and the oil yield.
• The choice of retention time is subject to parameters, such as temperature, heating rate,
and catalyst. A short retention time can lead to the partial decomposition of biomass,
whereas a long retention time can encourage the repolymerization and cracking of oil
into char and gas.
Much progress has been made on the HTL process. The capability of the HTL process
to convert biomass to produce high-energy biofuels has been proven without question. As
it stands, more research is needed on the pilot scale facilities, optimization of parameters for
a continuous process, understanding the physical properties of oil and, most importantly,
developing more robust upgrading and distillation techniques.

6. Challenges and Future Scope

In last two decades, HTL has more than proved that it is a highly efficient was to
convert biomass to biofuels and value-added chemicals. Compared to other biomass
conversion technologies, such as pyrolysis and gasification, HTL is reasonably new. The
technology must overcome many challenges at both the experimental and theoretical stages,
which leads to a range of future research possibilities.
• Some feeds with low overall conversion and poor bio-oil yield during HTL show
very promising results in the presence of another class of feedstocks. The research
on co-liquefaction is sparse; thus, more can be done to examine the co-liquefaction of
two or more feedstocks to improve the understanding of their synergistic effect on
bio-oil yield.
• The heating value of bio-oil is low compared to that of conventional liquid fuels,
which limits its applications. The low heating value is directly related to the high
oxygen content. Hence, there is a need to develop new methodology and techniques
to upgrade the bio-oil produced from HTL.
• Both bio-oil and char obtained from HTL contain a significant portion of heterogeneous
compounds with nitrogenous impurities. A study can focus on understanding the
reaction pathways of major impurities, such as nitrogen, to clarify its biodegradability
and toxicity.
• Apart from the experimental section, not enough research has been conducted on the
theoretical aspects of the HTL process:
◦ Establishing a correlation for similar types of feedstocks by doing regres-
sion analysis.
◦ Developing simulation models using computation fluid dynamics to develop
more insight into the effect of the physical properties of biomass water slurry
and the effect of various parameters in a continuous pilot scale process.
◦ Utilizing the concept of molecular dynamic simulations to develop a more
cohesive understanding on the reaction pathways; such investigations are war-
ranted.
◦ Understanding the techno-economic analysis of commercializing the HTL
process and extending it from production all the way through to distillation. A
life cycle assessment of the process is further suggested.
◦ More robust understanding about co-processing of bio-oil can be acquired
using detailed aspen models on the distillation process.
Energies 2021, 14, 4916 48 of 54

Author Contributions: Writing—original draft preparation, A.M. and S.D.; formal analysis, A.M.;
data curation: A.M.; writing—review and editing, A.M., D.P., M.K. and R.G.; resources, D.P. and
M.K.; supervision, D.P., M.K., A.K. and R.G.; funding acquisition, A.K. and R.G. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors thank the Future Energy System—Canada First Research Fund,
University of Alberta, Edmonton, Canada for supporting this study.
Conflicts of Interest: The authors declare no conflict of interest.

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