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Catalytic wet torrefaction of lignocellulosic biomass: An overview with

emphasis on fuel application

Frederick Jit Fook Phang , Megan Soh , Deni Shidqi Khaerudini ,

Gerald Ensang Timuda , Jiuan Jing Chew , Bing Shen How ,
Soh Kheang Loh , Suzana Yusup , Jaka Sunarso

PII: S1026-9185(22)00094-4
DOI: https://doi.org/10.1016/j.sajce.2022.10.008
Reference: SAJCE 354

To appear in: South African Journal of Chemical Engineering

Received date: 13 July 2022

Revised date: 26 September 2022
Accepted date: 24 October 2022

Please cite this article as: Frederick Jit Fook Phang , Megan Soh , Deni Shidqi Khaerudini ,
Gerald Ensang Timuda , Jiuan Jing Chew , Bing Shen How , Soh Kheang Loh , Suzana Yusup ,
Jaka Sunarso , Catalytic wet torrefaction of lignocellulosic biomass: An overview with em-
phasis on fuel application, South African Journal of Chemical Engineering (2022), doi:
https://doi.org/10.1016/j.sajce.2022.10.008

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Catalytic wet torrefaction of lignocellulosic biomass: An overview with emphasis on fuel application

Frederick Jit Fook Phanga,1, Megan Soha,1, Deni Shidqi Khaerudinib, Gerald Ensang Timudab, Jiuan Jing

Chewa, Bing Shen Howa, Soh Kheang Lohc, Suzana Yusupd, Jaka Sunarsoa,*

a
Research Centre for Sustainable Technologies, Faculty of Engineering, Computing and Science,

Swinburne University of Technology, Jalan Simpang Tiga, 93350 Kuching, Sarawak, Malaysia
b
Research Center for Advanced Materials, National Research and Innovation Agency (BRIN), Bld. 440

Kawasan Puspiptek Serpong, South Tangerang 15314 Banten, Indonesia

c
Energy and Environmental Unit, Engineering and Processing Division, Malaysian Palm Oil Board, 6,

Persiaran Institusi, Bandar Baru Bangi, 43000 Kajang, Selangor, Malaysia

d
Generation Unit (Fuel and Combustion Section), TNB Research Sdn. Bhd., No. 1, Kawasan Institusi

Penyelidikan, Jalan Ayer Hitam, 43000 Kajang, Selangor, Malaysia

Highlights

 Review of studies on catalytic wet torrefaction/hydrothermal carbonisation.

 Effects of different operating parameters towards biomass-derived hydrochar.

 Effects of various catalysts on derived hydrochars and carbon materials.

 Secondary formation role on improving the hydrochar’s fuel property.

1
These authors contributed equally to this work. *Corresponding author; Tel: +6082260709; Fax:
+6082260813; E-mail addresses: barryjakasunarso@yahoo.com; jsunarso@swinburne.edu.my (J.
Sunarso)
Abstract

Wet torrefaction (WT), also named hydrothermal carbonisation (HTC), has been regarded as one of

the highly studied thermochemical process pathways for biomass-to-solid fuel conversion in the last

decade (2012-2021). Catalysts have been added in the WT or HTC of lignocellulosic biomass for

various applications (i.e. solid fuel synthesis, carbon material synthesis, pre-treatment, sugar

production, ash content removal, and the study of reaction kinetics). Regardless, there is no review

on the addition of catalysts in WT to produce hydrochar as fuel, specifically on the role of catalysts in

the formation of ‘secondary deposits’, which refers to deposits that were observed on the

hydrochar. This review discusses the fundamentals of WT and how the lignocellulosic biomass

components in various biomass, operating process parameters, and catalysts affect the fuel property

of the hydrochar product. For catalytic WT and HTC, relevant studies in different yet interrelated

applications are overviewed, where insights are given based on the effect of catalyst addition on the

properties of hydrochar and the promotion of ‘secondary deposits’. The ‘secondary deposits’

established in carbon material synthesis studies can reveal the relationship between catalyst

addition and formation. On top of that, it also serves as a complimentary knowledge to enhance the

understanding of how these deposits can be used to increase the higher heating value of the

hydrochar, which is lacking in the existing hydrochar synthesis studies. Therefore, the aim of this

review is to provide insights into the addition of catalysts for the synthesis of hydrochar for fuel

application.

Keywords: Biomass; Catalyst; Hydrothermal carbonisation; Mechanism; Wet torrefaction.

Table of Contents

1 Background..................................................................................................................................... 5

2 Wet torrefaction of lignocellulosic biomass................................................................................. 16

2.1 Fundamentals of wet torrefaction ........................................................................................ 16

2.2 Effect of lignocellulosic biomass compositions as feedstocks for fuel synthesis ................. 18

2
 2.3 Effect of operating conditions on the fuel properties .......................................................... 21

2.3.1 Temperature ................................................................................................................. 21

2.3.2 Residence time .............................................................................................................. 23

2.3.3 Biomass-to-liquid ratio.................................................................................................. 25

2.3.4 Pressure......................................................................................................................... 26

2.3.5 Heating methods ........................................................................................................... 28

3 Catalytic wet torrefaction of lignocellulosic biomass .................................................................. 40

3.1 Introduction of catalyst in wet torrefaction and similar processes ...................................... 40

3.2 Solid catalysts ........................................................................................................................ 41

3.3 Liquid catalysts ...................................................................................................................... 42

4 Addition of catalysts in wet torrefaction for hydrochar synthesis............................................... 44

4.1 Acid catalysts......................................................................................................................... 44

4.1.1 Mineral acids ................................................................................................................. 44

4.1.2 Organic acids ................................................................................................................. 44

4.2 Salt catalysts.......................................................................................................................... 48

4.2.1 Chloride salts ................................................................................................................. 48

4.2.2 Triflate salts ................................................................................................................... 50

4.3 Others ................................................................................................................................... 51

5 Addition of catalysts in hydrothermal carbonisation for carbon materials synthesis ................. 63

5.1 Acid catalysts......................................................................................................................... 63

5.1.1 Mineral acids ................................................................................................................. 63

5.1.2 Organic acids ................................................................................................................. 66

5.2 Salt catalysts.......................................................................................................................... 71

5.2.1 Chloride salts ................................................................................................................. 71

5.3 Others ................................................................................................................................... 74

6 Addition of catalysts in other applications................................................................................... 80

6.1 Sugar production................................................................................................................... 80

6.2 Pre-treatment ....................................................................................................................... 82

3
 6.3 Ash content removal ............................................................................................................. 83

6.4 Reaction kinetics ................................................................................................................... 84

7 Lesson Learnt and Outlook........................................................................................................... 87

8 Conclusion and Recommendation ............................................................................................... 93

Declaration of Competing Interest ....................................................................................................... 95

Acknowledgements............................................................................................................................... 95

References ............................................................................................................................................ 95

4
Background

Renewable energy plays an important role in ensuring global energy security, reducing greenhouse

gas (GHG) emissions, as well as creating a circular economy to ensure resource efficiency. Many

countries have since moved towards utilisation of renewable alternatives such as hydro energy, solar

energy, and biofuels as part of the Nation’s energy mix to sustain the energy demand. For instance,

global electricity generated via renewable energy increased from 20.4 to 28.3 % from 2011 to 2021,

with an increase of 8 % over the decade (Gibb et al., 2022). However, transitioning from fossil fuel to

renewable energy sources for energy production remains challenging given the need for inherent

technologies, geological suitability, technology maturity, supply chain, and policy framework

adaptation. an innovative and thorough approach would be required to transit successfully, where

each approach is tailored specifically to respective renewable energy and its technology (Gielen et

al., 2019). Before these technologies can be fully realised, fossil fuels will still constitute a vast

portion of the global energy supply. Hence, research and effort are growing in pursuit of a fully

functional renewable energy application.

Renewable energy sources, in their direct utilisation in existing facilities, were also looked into to

ease the transition. A widely studied example is the co-firing of coal-biomass. Its application allows

the integration of a renewable energy source into an existing facility while being less

environmentally polluting (Xu et al., 2020b). In such applications, biomass is usually treated (i.e.

treated via biochemical or thermochemical processes) prior to combustion to enhance its fuel

properties (Casau et al., 2021). Thermochemical process, in particular, has received considerable

attention in treating lignocellulosic biomass wastes due to its effectiveness and ease of control. It

also provides flexibility in terms of the different alternative pathways (i.e. carbonisation, pyrolysis,

gasification, etc.). The advantages of lignocellulosic biomass waste (i.e. second-generation biomass

(Dahman et al., 2019) for fuel production through thermochemical conversion processes lie in the

fact that it is renewable, carbon-neutral, abundant, easy to source, and allows for holistic waste

5
management. Unlike first-generation biomass (i.e. edible biomass such as corns, seeds, grains, and

etc.), there are no ethical concerns on the utilisation of second-generation lignocellulosic biomass

waste (i.e. overexploitation of specific resources that may cause biodiversity loss (Singh et al.,

2021)). Nonetheless, using biomass as precursors is challenging due to its inherent properties. These

properties are high moisture content, low bulk density, complex and diverse structure, low energy

content, and recalcitrant nature (Irmak, 2019). Moisture content, in particular, was highly

problematic, as biomass with high moisture content hinders the conversion process’ effectiveness.

Biomass with high moisture content is more prone to moulding, biological degradation, and loss of

carbohydrates (organic content) (Johansson et al., 2006). In most treatment processes, the moisture

content of biomass of less than 20 % is preferred, making drying a necessary step to maximise

conversion efficiency (Irmak, 2019). Drying biomass requires an intense amount of energy,

ultimately reducing the overall energy efficiency of the process.

One of the potential technologies to address such shortcomings of biomass prior to subjecting to

thermochemical conversion is wet torrefaction (WT) or otherwise known as hydrothermal

carbonisation (HTC). WT or HTC can be defined as a treatment or conversion of precursor that occurs

in a liquid medium into hydrochar (Figure 1). The terms WT and HTC used depends on the targeted

product application, with WT focusing on the synthesis of coal-like biofuel, while HTC focuses on the

synthesis of carbonaceous materials (He et al., 2018). The usage of the aforementioned terms will

be adapted in this review. WT can be applied as a pre-treatment or treatment technology for

biomass as it is highly versatile for various feedstock applications, especially for biomass with high

moisture content. Since WT process occurs in a liquid medium, pre-drying biomass is unnecessary

(He et al., 2018).

6
 Figure 1. Schematic illustration of wet torrefaction or hydrothermal carbonisation.

To maximise the potential of WT and HTC-derived hydrochar, researchers have studied the addition

of catalysts in the aforementioned process. The addition of catalysts was shown to enhance the

properties of derived hydrochar. In the synthesis of carbon materials, addition of catalysts was

generally reported to provide positive results in both WT (i.e. enhanced hydrochar yield and HHV

(Ameen et al., 2022; Faradilla et al., 2021; Hasan et al., 2021)) and HTC (i.e. enhanced formation of

secondary deposits (Qi et al., 2016), enhanced morphology such as increased specific surface area

(Susanti et al., 2019), and etc.). The formation of these secondary deposits, which were the

polymerisation of components in the liquid medium onto the primary hydrochar, was also observed

in WT process (Ameen et al., 2022).

Figure 2 shows that the interest in catalytic WT and HTC has consistently risen since 2012 as

reflected by the general increase in the number of research articles and patents. These existing

research papers cover an extensive range of topics in the field of WT and HTC technologies

(including nano-carbon, activated carbon, catalyst, and supercapacitors). There are around 25 review

articles on the WT or HTC of biomass in the presence of catalysts (Table 1). Some of these review

articles compare other thermochemical technologies such as liquefaction, gasification, torrefaction,

acid-washing treatment with HTC as well as discuss the downstream application of the resulting

hydrochar such as in agricultural utilisation or production of bio-oil through pyrolysis, for instance.

7
Other than that, different types of hydrothermal processing were discussed as well (i.e.

hydrothermal liquefaction (HTL) and hydrothermal gasification or supercritical water gasification

(HTG or SCWG). The types of feedstocks and the effect of their properties are also discussed in these

review papers as a main aspect of HTC process, including livestock manure, municipal solid waste,

sewage sludge, plastic waste, and micro algae. These review articles focus primarily on a diverse

range of biomass in non-fuel applications (i.e. activated carbon, carbon materials), with some

consisting of brief sections on catalysts addition. This review aims to present a comprehensive

overview of the various types of catalysts used for WT and HTC of lignocellulosic biomass for various

reported applications, emphasising the insights that can be linked to the enhancement of fuel

properties for synthesised hydrochar as fuel. This review article is divided into two parts: (1) the WT

of lignocellulosic biomass for fuel application, and (2) insights on the addition of catalyst in biomass

WT in different applications and their implication in fuel applications. A brief discussion on non-

catalytic WT is given to facilitate structured progression and self-sufficient review work for non-

specialist readers.

Figure 2. Classification of various catalysts for wet torrefaction or hydrothermal carbonisation and

number of research articles (Scopus) and patents (Google Patents) in catalytic wet torrefaction or

hydrothermal carbonisation between 2012 and 2021.

8
 Table 1. Summary of existing review articles on wet torrefaction or hydrothermal carbonisation of

biomass in the presence of catalysts.

Author(s) Scope Content

Catenacci et al. Integration of pyrolysis  Investigation of the effect of different

(2022) and HTC with anaerobic precursors or substrates (i.e. sewage sludge,

digestion, where residues or wastes of agriculture and food

leftovers (digestate) origin, and animal manures), their

from anaerobic characteristics, and the quality of char

digestion were produced from different precursors

subjected to pyrolysis  Application of the derived char on

or HTC. agriculture, energy, adsorbent, catalysts,

and electrochemistry

 Recommendation on the expansion of

application

Karatas et al. (2022) Agricultural application  Quantification of phytotoxic organic

of HTC-derived compounds based on precursor

hydrochar from  Proposal and comparison of methods on

biomass. reduction of phytotoxicity

He et al. (2022) Production of carbon  Evaluation of synthesis technologies

materials from (hydrothermal carbonisation, reverse

liquefiable biomass (i.e. emulsion, sol-gel, and spray drying)

bio-oil, carbohydrate  Evaluation of CO2 capture performance of

solution, microalgae) derived carbon materials

9
  Perspective on scaling up of technology

Li et al. (2021) Synthesis technology  Synthesis technologies and effect of

for biomass of operating parameters

agriculture and forest  Prospects on new ideas and technical

origin insights

Marzbali et al. Hydrothermal  Comparison of HTC, HTL, and HTG

(2021) processing (HTC, HTL,  Summary of modelling work

and HTG) of wet wastes  Techno-economic analyses

(i.e. municipal solid  Recommendation regarding commercial

waste, sewage sludge, viability and environmental sustainability

algae, and food waste)

Masoumi et al. Evaluation of hydrochar  Characteristics of derived hydrochar

(2021) derived from HTC of  Reaction mechanism of hydrochar

waste biomass formation

 Activation and functionalisation of

hydrochar

 Applications of hydrochar (i.e. agricultural

usage, adsorbent, energy, carbon capture,

electrochemistry, and catalyst)

MacDermid-Watts Catalytic HTC on the  Effect of catalyst addition on the synthesis

et al. (2021) synthesis of activated of activated carbon from HTC based on the

carbon degree of carbonisation, modification of the

surface, and heteroatoms doping

10
Khan et al. (2021) HTC of precursor such  Evaluation of the suitability of precursor

as biomass of woody, material in the HTC process

plant, and agriculture  Effect of operating parameters on HTC

origin, algae, and derived hydrochar (i.e. temperature, time,

municipal solid waste liquid pH, and biomass-to-liquid ratio)

 Conversion mechanism of biomass

constituents

 Prospects on hydrochar application (catalyst

and adsorbent) and effect of HTC

parameters

Suresh et al. (2021) Conversion technology  Lignin’s availability in the region of interest

of lignin (sub-continent of India)

 Evaluation of conversion technology with

lignin precursor (i.e. pyrolysis, HTC, HTL,

catalytic fast pyrolysis, hydrotreatment, and

hydrodeoxygenation)

Adolfsson et al. Application of  Exploration of applications on the

(2020) hydrochar derived from hydrochar such as catalysts, flame

HTC of cellulose retardants, antibacterial materials, and

functional fillers in bioplastic composites)

Khan et al. (2019) HTC of lignocellulosic  Effect of operating parameters on HTC

biomass for the derived hydrochar (temperature, time,

synthesis of carbon liquid medium pH, heating rate, biomass-to-

materials liquid ratio)

11
  Elaboration of reaction mechanism

(hydrolysis, dehydration, decarboxylation,

and carbonisation)

 Application of hydrochar as additives, fuels,

catalysts, and electrochemistry

Zhao et al. (2019) Synthesis of carbon  Evaluation of methods for carbon materials

materials from wood synthesis (i.e. HTC, direct carbonisation, and

liquefaction-carbonisation), with emphasis

on liquefaction

 Characteristics of carbon materials obtained

via liquefaction (morphology, and porosity)

based on different methods (i.e. doping,

nano-etching, doping, soft template, and

ultrasonic spray pyrolysis)

 Recommendation to explore hydrochar’s

application in supercapacitors

Mathimani and Hydrothermal  Review on types of hydrothermal energy

Mallick (2019) technologies on the utilised in the conversion of microalgal

conversion of biomass (HTC, HTL, and HTG)

microalgal biomass  Effect of operating parameters in HTL of

microalgal biomass

Cao et al. (2018) Conversion technology  Recent advances in lignin utilisation

of lignin  Conversion of lignin into value-added

products via various processes (HTC, HTL,

12
 catalytic degradation, hydrogenolysis, and

pyrolysis)

Cheng and Li (2018) Synthesis of char from  Effect of the operating parameter (emphasis

pyrolysis and HTC of on temperature) and nature of precursor on

biomass synthesised char

 Insights on modification of char (surface

functionalisation, composites formation, in

situ heteroatom doping, and activation)

 Application of char as a catalyst in biomass

hydrolysis and bio-diesel production

Sharma et al. (2018) Synthesis of char from  Effect of operating parameters on char

pyrolysis and HTC of based on reviewed process (pyrolysis and

biomass HTC)

 Comparison of pyrolysis and HTC to dry

torrefaction and gasification

 Application of char based on

physicochemical properties (i.e. catalyst,

fuel cell, adsorbent, activated carbon, soil

amendment, and etc.)

 Environmental and agricultural advantages

of char application

Krylova and HTC of biomass  Conversion of precursor with different

Zaitchenko (2018) properties into char via HTC, dry

torrefaction, and pyrolysis

13
  Reaction mechanism of HTC

 Characteristics of hydrochar

 Application of derived hydrochar (catalyst,

adsorbent, fuel)

Nizamuddin et al. HTC of biomass  Effect of operating parameters on

(2017) hydrochar synthesis (temperature, time,

pressure, catalyst, and precursor type)

 Characteristics of synthesised hydrochar

Cha et al. (2016) Synthesis and  Review of char synthesis processes (HTC,

application of char pyrolysis, gasification, and etc.)

 Application of synthesised char as catalyst,

adsorbent, soil conditioner, supercapacitor,

fuel cell, and hydrogen storage.

Wu et al. (2016) HTC of biomass  Effect of temperature and precursor

biomass properties on synthesised

hydrochar

Deng et al. (2016) Application of biomass  Recent advances of biomass derived carbon

derived carbon materials in fuel cells, lithium-ion batteries,

materials supercapacitors, and water splitting devices

via electrocatalysis.

 Synthesis of carbon materials via pyrolysis,

ionothermal carbonisation, and HTC

 Formation mechanism of carbon materials

14
Patel et al. (2016) Hydrothermal  Evaluation of hydrothermal technologies

technologies on the (HTL, HTC, HTG) on the conversion of algal

conversion of algal biomass into value-added products

biomass  Application of hydrothermal process liquid

as an extraction medium and

hydrotreatment of algal biocrude

 Life cycle assessment on current cutting-

edge technologies

Huang and Yuan Hydrothermal  Evaluation of hydrothermal technologies

(2016) technologies for the (HTL, HTC, HTG)

treatment of sewage  Methods for the determination of heavy

sludge metal contamination level and risk

 Transformation and migration behaviour of

heavy metals based on operating

parameters (temperature, time, additives,

solvent type)

Jain et al. (2016) Application of  Recent advances in the synthesis of

hydrochar derived from activated carbon via hydrochar precursor

biomass waste as obtained from hydrothermal carbonisation

activated carbon of biomass waste

 Effect of operating parameters

(temperature, time, biomass-to-liquid ratio,

and catalyst) on surface characteristics of

hydrochar

15
 Liu et al. (2015) Hydrolysis of cellulose  Synthesis of solid acid catalysts and their

with solid acid catalyst mechanism

 Operating parameters of cellulose

hydrolysis

 Application of product obtained from

cellulose hydrolysis

Wet torrefaction of lignocellulosic biomass

This section focuses on WT for hydrochar and the factors that govern the WT of lignocellulosic

biomass to produce fuel. It should also be noted that wet-torrefied biomass or the fuel product is

denoted as hydrochar throughout this review.

Fundamentals of wet torrefaction

WT is a treatment process that occurs in a liquid medium, whereby biomass are upgraded to carbon-

rich hydrochar with improved fuel properties (i.e. higher HHV, hydrophobic, and etc.) in an autoclave

under hot-compressed water or subcritical water condition or an enclosed high-pressure reactor

(Figure 3). WT is typically performed between 180-260 oC with pressure increased autogenously up

to 4.6 MPa gauge (Lynam et al., 2011). Nonetheless, some studies have performed WT at

temperatures of up to 375 oC, while residence time used for the process can vary from 5 minutes to

several hours. Some literature reported WT as HTC, and these terms are used interchangeably.

Although HTC uses the same principle of processing biomass in hot-compressed water or under

subcritical water conditions as in WT, originally, HTC was used to convert biomass to carbonaceous

materials and its derivatives such as supercapacitors for energy storage, bio-adsorbent, catalyst, and

etc. It is worth noting that HTC covers a wide range of applications for biomass conversion (i.e.

16
carbon material synthesis, activated carbon, catalyst, and etc.). But WT focuses specifically on using

the process to treat biomass into solid fuel (i.e. hydrochar) (Bach & Skreiberg, 2016).

Figure 3. Schematic illustration on generally used experimental setups for WT or HTC of

lignocellulosic biomass feedstocks, where (a) is an autoclave (i.e. acid digestion vessel (Parr, 2016)),

which is usually placed in a temperature controlled oven and operates in an autogenous pressure

condition, and (b) a reactor with temperature and pressure control and operates in a controlled

pressure condition (Bach & Skreiberg, 2016) (reproduced from Parr (2016) and Bach & Skreiberg

(2016)).

Water plays an essential role in WT process as its properties at high temperatures (i.e. reduced

dielectric constant and polarity) mimic that of organic solvents (Carr et al., 2011; Coym & Dorsey,

2004; Pauline & Joseph, 2020). Water produces hydronium and hydroxide ions under auto

ionisation, and the degree of dissociation of the hydrogen bond in water molecules increases by 3-

fold under subcritical conditions. Hence, this reduces the pH of the water, causing accelerated

reactions that favours acidic condition such as hydrolysis of hemicellulose (Kambo & Dutta, 2015;

Yang, 2007). WT involves a series of multiple parallel reactions given biomass's complex structure

and composition and the variation of the liquid medium properties under different operating

conditions. For example, WT of cellulose yields organic acids such as acetic acid, formic acid, and

levulinic acid, which further decreases the pH in the liquid medium during WT and henceforth,

17
further promoting other side reactions to the biomass (Funke & Ziegler, 2010). As such, the addition

of catalysts can promote accelerated reactions and be more cost-effective relative to increasing the

reaction severity by subjecting to higher operating parameters.

Effect of lignocellulosic biomass compositions as feedstocks for fuel synthesis

Biomass is a broad term referring to various types of materials. Some examples (but not limited to)

are lignocellulosic biomass (i.e. biomass of plant origin, primarily composed of cellulose,

hemicellulose, and lignin), food wastes, aquatic biomass (i.e. algal plants), and wastes of animal

origins (i.e. manures). Lignocellulosic biomass were widely utilised as precursors in WT or HTC, hence

will be emphasised in this work. It is essential to understand the effect of biomass composition on

the fuel properties when lignocellulosic biomass is a precursor. Thus this review focuses on the

literature works with lignocellulosic biomass and their lignocellulosic components (i.e. cellulose) as

the precursor materials. The three primary components of lignocellulosic biomass are cellulose,

hemicellulose, and lignin. The fuel quality of hydrochar can generally be predicted based on an

understanding of the lignocellulosic components in the biomass, assuming the absence of impurities

(Demirbaş, 2001).

The mass yield and HHV of the hydrochar primarily depend on the lignin content of the precursor

biomass in WT. This is due to the resistance of lignin to thermal degradation when compared to

cellulose and hemicellulose. Lignin is generally a desirable component in biomass WT, given its

higher HHV than cellulose and hemicellulose. For instance, Demirbaş (2001) reported that the HHV

of lignin ranges between 23.26 to 25.58 MJ kg-1, while cellulose and hemicellulose have a HHV of

approximately 18.60 MJ kg-1. Kim et al. (2017) also reported a similar observation, where cellulose,

hemicellulose, and lignin exhibited HHVs of 16.5, 13.8, and 20.4 MJ kg-1, respectively. Demirbaş

(2001) studied the correlation between HHV and lignin composition for 14 types of biomass and

proposed equations for HHV estimation purely based on the lignin content. They concluded that the

relationship between lignin content and the HHV of the biomass is linear, supporting the fact that

18
the HHV of hydrochar is primarily dependent on lignin composition. Lignocellulosic biomass can be

divided into various subcategories as well, such as (but not limited to) fronds, hulls, leaves, peels,

shells, stalks, straws, wood (hardwood and softwood), and others (i.e. residue such as corn cob or

empty fruit bunches, and etc.). Table 2 lists the relative amount of cellulose, hemicellulose, and

lignin for several commonly found lignocellulosic biomass from literature. Biomass with high lignin

content generally have higher average HHV. Olive cake and hazelnut shell with lignin content of

55.29 and 43.01 %, respectively, had HHV of 21.53 and 20.05 MJ kg-1, respectively (Demirbaş, 2001).

Regardless, while these reported biomass generally abide by this trend, some reported properties of

biomass can be different. For instance, Reza et al. (2015) studied wheat straw with a lignin content

of only 11.69 wt. %, but had HHV of 20 MJ kg-1. Hence, the HHV of raw biomass generally varies on a

case-by-case basis.

Table 2. The composition of lignocellulosic components and HHV for several common biomass

(extractive free and ash free basis).

Cellulose Hemicellulose Lignin HHV

Types Species Ref
-1
( %) ( %) ( %) (MJ kg )

Fronds Oil palm fronds 34.07 21.98 43.96 16.00 (Ameen et al., 2022)

41.00 38.07 20.92 - (Loh, 2017)

Hull Soybean hulls 66.71 27.32 5.96 - (Faradilla et al., 2021)

Leaves Oil palm leaves 20.60 17.10 62.30 17.20 (Ameen et al., 2022)

Tobacco leaf 43.45 41.54 15.01 17.70 (Demirbaş, 2001)

Peel Potato peel 68.04 14.42 17.54 - (Lenihan et al., 2010)

Shell Hazelnut shell 26.70 30.29 43.01 20.05 (Demirbaş, 2001)

19
 Palm kernel shell 44.50 23.00 32.50 17.20 (Ameen et al., 2022)

21.99 24.23 53.78 - (Loh, 2017)

Stalk Cornstalk 44.17 47.57 8.27 - (Zawawi et al., 2013)

Tobacco stalk 44.32 28.89 26.79 18.43 (Demirbaş, 2001)

Straw Corn straw 51.53 30.88 17.59 18.27 (Demirbaş, 2001)

Rapeseed straw 50.95 28.16 20.88 - (Rozenfelde et al., 2021)

49.60 26.27 24.13 - (Lu et al., 2009)

Wheat straw 33.82 45.20 20.98 18.55 (Demirbaş, 2001)

42.70 45.61 11.69 20.00 (Reza et al., 2015)

Wood Ailanthus wood 47.52 26.73 25.75 19.37 (Demirbaş, 2001)

Beechwood 46.27 31.86 21.87 19.23 (Demirbaş, 2001)

Hardwood 45.85 32.26 21.89 18.97 (Demirbaş, 2001)

Oil palm trunks 44.36 34.04 21.60 - (Loh, 2017)

Softwood 42.68 24.82 32.50 19.55 (Demirbaş, 2001)

Spruce wood 47.11 21.31 31.58 19.77 (Demirbaş, 2001)

Others Corncob 52.49 32.32 15.19 17.48 (Demirbaş, 2001)

Empty fruit 46.92 32.79 20.29 - (Loh, 2017)

bunches

Loblolly pine 59.41 13.09 27.50 19.90 (Lynam et al., 2011)

Olive cake 23.08 21.63 55.29 21.53 (Demirbaş, 2001)

20
Effect of operating conditions on the fuel properties

Temperature

Temperature represents a critical operating parameter for WT of biomass as it reflects energy in the

form of heat to disintegrate the biomass particle and controls the water properties for ionic and

radical degradation reactions (Pauline & Joseph, 2020). Increasing the temperature alters the water

viscosity in ionic dominated reactions (i.e. from the viscosity of 1.8 mPa∙s at 0 oC to 0.14 mPa∙s at

350 oC). This viscosity reduction enhances the liquid medium's penetration into the porous structure

of the biomass, further promoting biomass degradation (Funke & Ziegler, 2010). Different

temperature range promotes the synthesis of different products. For example, higher char yield is

generally obtained below 250 oC. Higher oil or liquid yield is obtained at moderate temperatures

below 375 oC. On the other hand, temperature above 375 oC favours gas yield (Nizamuddin et al.,

2017).

Table 3 compiles the proximate analysis, ultimate analysis, higher heating value (HHV), and solid

yield for various biomass and hydrochars at different operating conditions (i.e. temperature, solid to

liquid ratio, and residence time) from literature. Table 3 shows that increasing the temperature,

even for a small increment of 20 oC, generally results in increased HHV for all types of biomass.

Furthermore, enhanced energy content of raw bamboo sawdust from 17.66 to 18.35 MJ kg-1 was

achieved by subjecting the bamboo sawdust to WT at a low temperature of 150 oC (Dai et al., 2017).

A study conducted by Nakason et al. (2018) on the WT of coconut husk and rice husk at a

temperature range between 140 and 200 oC revealed that increasing the operating temperature

(140 to 200 oC) increases the fuel ratio, which is expressed as fixed carbon content over the volatile

matter content. Such an increase in the fixed carbon content led to increased HHV. They also

observed solid yield loss with increasing temperature due to biomass degradation via hydrolysis and

deoxygenation reaction. The HHV also highly correlates with the biomass's carbon, hydrogen,

oxygen, and nitrogen contents. Aguado et al. (2020) performed assays on the WT of almond tree

21
pruning and reported enhanced HHV from 18.64 to 28.50 MJ kg-1 and 19.26 to 29.32 MJ kg-1 when

the temperature was increased from 175 to 300 oC at residence time of 10 and 60 minutes,

respectively. They attributed such increment in HHV of wet torrefied biomass to the concentrated

carbon content and decreased oxygen content from dehydration reaction. They also suggested that

reduction in oxygen content mainly comes from degradation of hemicellulose and cellulose as these

two components are oxygen-rich relative to lignin. This led to the reduced solid yield with

temperature rise.

Nonetheless, WT at a certain temperature range does not significantly change the fuel properties of

the resultant hydrochar. Volpe and Fiori (2017) studied the temperature role in WT of two types of

olive waste, i.e. olive tree trimmings and olive pulp. They utilised temperature that varies from 120

to 250 oC. They found that WT of these two olive residues at 120 and 150 oC gave insignificant mass

loss and a meagre increase in HHV (Table 3). The low increment in HHV of the olive residues after

WT at low temperatures of 120 and 150 oC was attributed to the removal of organic and inorganic

extractives that barely contributed to HHV of the samples. On the other hand, Yuliansyah et al.

(2010) reported that O and H reduction on the WT of oil palm trunks and oil palm fronds at 200-350
o
C with an initial pressure of 2.0 MPa was more pronounced between 200-270 oC with marginal

change above 270 oC. In terms of energy content, they reported that oil palm trunk hydrochar and

oil palm frond hydrochar attained a maximum HHV of 29.7 MJ kg-1 after WT at 350 oC. However,

similar to their observation of the O and H content reduction, the HHV improvement was more

obvious within temperature range of 200 to 270 oC. The relative amount of biomass components

that can be hydrolysed is affected by temperature, as hemicellulose and cellulose are completely

hydrolysed at 180 and 220 oC, respectively (Pauline & Joseph, 2020). At low temperature ranges,

only marginal change is observed since sufficient heat from increased temperature is necessary to

overcome the energy barrier and utilise ample activation energy to break up the biomass structure

to attain higher concentrations of free radicals (Kumar et al., 2018). Increasing the temperature

further would only result in marginal degradation of lignin, which is more thermally stable than

22
cellulose and hemicellulose. Yang et al. (2015) found that lignin-rich Calophyllum inophyllum has the

least HHV increment compared to Plumeria alba and Humulus lupulus. This is since hemicellulose

and cellulose can be degraded at a lower temperature range, resulting in lignin-dense hydrochar

with high HHV. Selecting the suitable range of temperature for WT of lignocellulosic biomass is thus

essentially important given the wide variation in the properties of different lignocellulosic biomass

to ensure efficient production and cost consumption.

Residence time

Residence time for the WT of lignocellulosic biomass is another major contributing factor to the

hydrochar fuel properties as it increases the reaction severity. Missaoui et al. (2017) investigated

the WT of dried olive pomace at different reaction times, i.e. 0, 5, 30, 60, and 120 minutes using a

batch reactor at 215 oC and water to biomass ratio of 6 by weight. They reported that the mass yield

obtained was minimum at 5 minutes and progressed to maximum mass loss of 61 % at 120 minutes.

They also found that when the sample was subjected to flash WT, i.e. for 0 minute at a water to

biomass ratio of 10 by weight, substantial yield of liquid phase was solubilised from the solid. This

was attributed to the solubilisation of hemicellulose and extractive into the liquid phase is favoured

at mild operating conditions. Chen et al. (2018) performed a WT study on sweet potato waste at 75

mL to 15 g water to sweet potato waste ratio at different operational parameters. Their

investigation on the effect of residence time at 0, 30, 60, 90, and 120 minutes showed decreasing

solid yield trend of 60.36, 56.83, 56.21, 54.39, and 53.45 %, respectively. Although the solid yield of

hydrochar decreased with increasing residence time, it was implied that reaction temperature still

has greater influence on the hydrochars’ yield as compared to the residence time. They also

observed slight reduction in carbon content when increasing the reaction time from 90 to 120

minutes, which is a result of secondary decomposition of the hydrochar. Similar observations were

made by Gao et al. (2016), who observed a marginal effect on the WT of eucalyptus bark with

varying residence times of 2, 4, 6, 8, and 10 hours. Soh et al. (2022) examined the effect of WT on oil

palm trunks at prolonged residence times of 3, 6, 9, 12, 18, 24, 48, and 72 hours at three operating

23
temperatures. Their findings revealed that solid yield loss became less significant beyond the 24-

hour operating time. They also observed logarithmic-like increment of the HHV of the oil palm trunk

hydrochar at all temperatures, of which at 220 oC, the HHV did not increase much further and

reached a plateau afterwards. Such a phenomenon could be attributed to the decomposition of

hemicellulose and cellulose within 24 hours of residence time, leaving a lignin-dense hydrochar.

Beyond 24 hours of residence time, lignin became the main constituent in the hydrochar, which

requires much longer residence time and higher temperature to decompose.

Although most studies have reported that temperature significantly influences the hydrochar

properties relative to residence time, the effect of residence time is still considerably high. Another

factor influencing the HHV of hydrochar is the formation of hydroxymethylfurfural (HMF), which has

a HHV of 22.06 MJ kg-1 in the hydrothermal media. HMF generally deposits onto the surface of the

hydrochar in the form of microspheres, thus increasing the HHV of hydrochar (Kambo & Dutta,

2015). Borrero-López et al. (2018) investigated the WT of hemicellulose, cellulose, and lignin at

different reaction temperatures and reaction times on the production of 5-hydroxymethyfurfural (5-

HMF or HMF). They reported that the formation of HMF from hemicellulose requires a lower

temperature relative to cellulose. On the contrary, the formation of HMF from hemicellulose

required a higher reaction time relative to cellulose. They reported that the HMF concentration

obtained from WT of hemicellulose peaked at 180 oC for the reaction time of 6 hours followed by

200 oC for the reaction time of 2 hours, while cellulose peaked at 220 oC for reaction time of 3 hours

followed by 240 oC for reaction time of 1 hour. Borrero-López et al. (2018) further revealed that

hemicellulose and cellulose are effective in producing HMF but the latter gave higher productivity

since glucose is a monomer of cellulose and is also the precursor of HMF. On the other hand, lignin is

not suitable for HMF production since lignin mainly produces phenolic compounds. Sevilla and

Fuertes (2009) observed microspheres with a diameter ranging between 2 and 10 µm from cellulose

hydrochar that was wet-torrefied above 220 oC. These microspheres were absent in the cellulose

hydrochar wet-torrefied below 220 oC. They hypothesised that these microspheres were formed

24
through the hydrolysis of cellulose to glucose, which underwent further dehydration and

fragmentation to form HMF. The HMF then underwent intermolecular dehydration or aldol

condensation to form microspheres. Kambo and Dutta (2015) postulated that the deposition of the

HMF microspheres could be enhanced by increasing the porosity and adsorption capacity of the

hydrochar.

Soh et al. (2022) observed that oil palm trunk hydrochar produced via WT at 220 oC for 72 hours

formed more microspheres compared to that produced at 220 oC and lower residence time. The

formation of these microspheres was attributed to the repolymerisation of HMF intermediate.

Compared to their previous study (Soh et al., 2020) of wet torrefied oil palm trunks at 240 oC for 3

hours, these findings indicated that prolonged residence time positively affects microsphere

formation. Ahmed Khan et al. (2019) performed the study to synthesise and characterised

carbonaceous material made from WT of rubber wood fibre under different operating conditions,

i.e. temperature, residence time, and water to biomass ratio. Their surface morphology analysis

using scanning electron microscope (SEM) revealed that the amount and the size of microspheres

formed increase with prolonged residence time. Relative to reaction temperature, the study on the

effects of residence time on lignocellulosic biomass is less explored. The residence time is an

essential parameter since secondary decomposition of hydrochar typically occurs and cross-reaction

can occur with the components dissolved in the liquid phase, which can be further promoted with

increasing reaction time.

Biomass-to-liquid ratio

Biomass-to-liquid ratio is another contributing factor to the properties of hydrochar especially the

HHV and solid yield of the hydrochars. The total liquid content is defined as the total mass of added

water and water (moisture) retained in the wet biomass (i.e. biomass that has not been dried)

(Shafie et al., 2018). Some study opted to dry the biomass prior to WT process (to ensure

consistency of the product and ease of storage) and reported the biomass-to-liquid ratio without

25
considering the moisture retained in the dried biomass (Yeoh et al., 2018). It should be noted that

biomass may still have a certain amount of bound moisture, which cannot be removed by the drying

process. Generally, the moisture content in biomass is classified as free moisture and bound

moisture. The free moisture is easier to evaporate relative to bound moisture due to their weaker

binding force with the biomass (Chen et al., 2012a). Yeoh et al. (2018) reported the effect of

biomass-to-liquid ratio on the HHVs of empty fruit bunches, mesocarp fibre, and palm kernel shell

that were wet torrefied at 220 oC for 1 hour. They reported that decreasing the biomass-to-liquid

ratio from 1:30 to 1:150 in WT of EFB decreases the hydrochar HHV by 9.55 %. Volpe and Fiori

(2017) reported that increasing the biomass-to-liquid ratio in the WT of olive trimmings and olive

pulp led to higher hydrochar yield. Higher biomass loading can promote back-polymerisation from

the organic components-rich liquid medium and the formation of secondary char that is rich in

thermally stable carbon. Missaoui et al. (2017) noted that WT of olive pomace at a low biomass-to-

liquid ratio of 1:10 gave higher solid yield and higher dissolved liquid fractions relative to the high

biomass-to-liquid ratios of 1:6 and 3:10 due to the higher solvent proportion that promotes the

solubilisation of biomass. The biomass-to-liquid ratio is an essential factor especially in the

commercialisation of WT for large-scale production, as the high amount of liquid waste formed

would require energy and cost-intensive treatment. However, the liquid fraction also contains a

substantial amount of dissolved organic matter and valuable side products that can be further

valorised and extracted.

Pressure

WT generally occurs at high pressure (0.8 to 4.3 Mpa (Gan et al., 2019)) and increasing the

temperature increases the internal pressure autogenously via the vapour pressure of water (Figure

4), thus accelerating the chemical reactions rate and reaction severity (Yan et al., 2019). Yan et al.

(2019) suggested that increasing the pressure during WT instead of temperature can bring similar

reaction effects to increasing temperature. They studied the effect of different pressures in the WT

of empty fruit bunches (i.e. 0.1, 1.3, and 3.1 MPa) at a fixed temperature and residence time of 180

26
o
C and 0.5 hours, respectively, on the resultant hydrochar fuel properties. They concluded that

elevating the pressure leads to a significant increment in the hydrochar’s higher heating value (HHV)

from raw empty fruit bunches of 18.3 MJ kg-1 to 22.2 and 23.6 MJ kg-1 in N2 and CO2 atmosphere,

respectively as well as ash reduction from 7.8 % to 2.4 and 2.3 % in N2 and CO2 atmosphere,

respectively. They noticed that elevating the pressure specifically to 3.1 MPa or above gives

comparable HHV relative to the hydrochars produced from conventional WT at higher temperature

(i.e. 220 to 250 oC) without pressurising the system in their previous works (Novianti et al., 2014;

Parshetti et al., 2013), which gave HHV in the range of 22.1-22.4 MJ kg-1 range. Nonetheless, when

comparing different pressurising gas, pressurising the system with N2 gave a more constant and

higher energy yield relative to using CO2 at all three pressures. This was attributed to CO2 reaction

with water, which leads to the formation of carbonic acid that can catalyse the decarboxylation

reaction of the biomass. This translates to lower solid yield and, subsequently, lower energy yield.

On the other hand, inert N2 does not react with the water medium but the pressure-induced helps to

promote the water medium to penetrate the biomass more easily. The effects of different reaction

atmospheres on the hydrochar fuel properties were also studied by Bach et al. (2015a). They

employed N2 and CO2 to pressurise the WT of Norway spruce and birch to 70 bar and treated it at

175, 200, and 225 oC for 30 mins, respectively. WT of the spruce and birch in N2 gave higher

resulting solid yields of 4.6-6.0 % and 4.4-5.5 %, respectively, compared to that obtained in CO2

atmosphere. They also reported that inducing the WT system with CO2 is more effective in reducing

the biomass ash content to a 60-69 % removal relative to using N2. In their study, however, in

contrast to the study conducted by Yan et al. (2019), the HHVs of the hydrochars produced from WT

in CO2 were lower relative to N2. Similarly, the energy yield of the solid hydrochars treated in CO2

atmosphere was also lower than that of in N2. Nonetheless, they reported that WT of spruce and

birch in CO2 improved the resulting hydrochar’s grindability and hydrophobicity more than in N2.

Thus, the selection of reaction atmosphere and pressurising gas highly depends on the desired

product properties. WT of biomass mainly emits three main components, i.e. solid fraction termed

27
hydrochar, liquid fraction, and a minor fraction of gas that consists primarily of CO2 (Wang et al.,

2018a). Thus, utilising CO2 as the catalysing and pressurising medium for WT allows further

utilisation of the emitted CO2 and recirculating back into the system for such application.

Figure 4. Water phase diagram (reproduced from Gan et al. (2019)).

Heating methods

Microwave is a form of electromagnetic radiation at a high frequency between 300 MHz and 300

GHz that interacts with molecules through dipolar rotation and ionic conduction to generate heat.

Most of the WT of lignocellulosic biomass uses conventional heating to heat the process. There are a

few studies that used microwave radiation as the form of heating for WT to improve the resultant

hydrochar fuel properties, including those that used sugarcane bagasse (Chen et al., 2012b),

rapeseed husk (Elaigwu & Greenway, 2016), coconut shells (Elaigwu & Greenway, 2019), fallen

28
leaves and deadwood (Shao et al., 2019), corn stalk (Hu et al., 2019; Kang et al., 2019), bamboo (Dai

et al., 2017; Li et al., 2015), and phoenix tree leaves (Xu et al., 2020a). In WT of biomass via

microwave heating, a 2.45 GHz frequency was employed in most studies with output power

between 500 and 1600 W.

Microwave WT of biomass is greatly affected by various operating parameters. To better understand

the effect of the different operating parameters, optimisation studies on the microwave-assisted WT

of biomass were conducted (Kang et al., 2019; Shao et al., 2019). In a study by Shao et al. (2019),

hemicellulose and cellulose-rich waste (i.e. fallen leaves and deadwood) was subjected to

microwave-assisted WT at 2.45 GHz frequency with a power of 800 W at 6 oC min-1 heating rate to

study the influence of the process temperature (130, 150, 170, and 190 oC), residence time (0.5, 1,

1.5, and 2 hours), and biomass to water ratio (1:7, 1:8, 1:9, and 1:10) on the resultant hydrochar’s

characteristics as well as to optimise the process conditions by response surface methodology

(RSM). Their investigations of the effects of temperature, biomass to water ratio, and residence time

revealed that the highest hydrochar HHV of 23.01 MJ kg-1 was obtained at the highest temperature

of 190 oC, biomass to water ratio of 1:8, and residence time of 1 hour. The increased temperature

led to partial decomposition of hemicellulose and cellulose, which leaves behind a lignin-rich

hydrochar (Kambo & Dutta, 2015). They further explained that residence time is an important factor

influencing the fuel property of the resulting hydrochar during microwave-assisted WT. Longer

contact time between the solid and the liquid that contains organic matter allows the organic matter

in the liquid phase to recombine back onto the hydrochar, as observed from the increased solid yield

above 1-hour residence time.

In another study, Kang et al. (2019) performed process parameters optimisation study on the

microwave-heated WT of corn stalk at varying temperatures, residence time, and solid to liquid ratio

that varies between 122.7 and 257.3 oC, 4.8 and 55.2 min, and 0.98 and 6.02 g/50 mL, respectively.

As expected, their results revealed increased solid yield loss with increasing heating temperature.

29
The reduction in solid yield was attributed to the cellulose hydrogen bond network weakening above

180 oC, thus causing the polar hydroxymethyl (CH2OH) groups to behave as “molecular radiators”

that subsequently cause the polysaccharide chain of cellulose to cleave and form glucose monomers

(Fan et al., 2013; Kang et al., 2019). On the contrary, they found that increasing the solid to liquid

ratio during microwave-heated WT of corn stalk gave higher solid yield since the increased solid

loading impedes the microwave penetration to disrupt the polysaccharides due to the limited

penetration depth of microwave irradiation (Budarin et al., 2015; Bundhoo, 2018; Kang et al.,

2019). In terms of energy content, the F values as given in ANOVA, which describes the difference

between the mean values of the energy content of the hydrochar under different parameters (i.e.

temperature, residence time, and solid to liquid ratio) showed that temperature and residence time

gave more prominent effect on mass yield than biomass-to-liquid ratio. As a result, increased

temperature promotes the decarboxylation reaction and thus decreases the biomass's oxygen

content, leading to higher energy content. The energy yield is an important property for fuel

application since it reflects the amount of energy retained in the hydrochar. Despite previous

findings that increasing temperature and residence time can significantly improve the hydrochar’s

energy content, it was found that the dominant factor that governs the energy yield of the

hydrochar is mainly temperature followed by solid to liquid ratio.

Dai et al. (2017) compared the conventional heating method with microwave radiation heating for

the WT of bamboo sawdust of moso bamboo at varying temperatures between 150 to 230 oC at 30

min for further pyrolysis application. Their study revealed that the hydrochar heated by microwave

radiation resulted in higher hydrochar mass yield, HHV, and energy yield at all three temperatures

(i.e. 150, 190, and 230 oC) relative to conventional heating. The relatively higher HHV of bamboo

sawdust hydrochar from microwave heating than conventional heating was caused by the hot spot

effect from microwave radiation that facilitates C-H and C-O bonds breakage at low energy.

Although microwave radiation can heat the whole material by penetrating the entire object

homogeneously simultaneously, hot spot effects whereby temperature is distributed non-uniformly

30
can occur depending on the penetration depth and surface heat loss. Although microwave radiation

has an insignificant influence on the hydrochar’s chemical structure, FTIR analysis revealed that the

acetyl in hemicellulose is more effectively ruptured and removed by microwave radiation. This leads

to reduced acetic acid content in the pyrolysis vapour, i.e. from 17.3 % in raw bamboo sawdust to

8.13 and 5.5 % in bamboo sawdust hydrochar heated by conventional heating and microwave

radiation, respectively. Furthermore, their Py-GC/MS results revealed that higher glucopyranose (a

precursor for various chemicals synthesis) content of 15.71, 36.50, and 43.30 % was obtained in the

pyrolysis vapour from bamboo sawdust hydrochar treated with microwave radiation at 150, 190,

and 230 oC, respectively compared to that from conventional heating which only gives

glucopyranose content of 15.60, 16.68, and 24.76 % at all three temperatures. Research works that

apply microwave heating in WT are still limited. Regardless, this review focuses on the catalytic WT

of lignocellulosic biomass; hence this section only serves as additional information.

31
Table 3. Compilation of proximate, ultimate, higher heating value (HHV), and solid yield of hydrochar derived from different types of precursor biomass at

different operating conditions.

Biomass Biomass- Temperature Residence Proximate analysis (wt. %) Ultimate analysis (wt. %) HHV Solid Ref

to-liquid Time Yield

mass

ratio

o
g:g C min Moisture Volatiles FC Ash C H N O S MJ kg-1 Wt. %

Rice husk - - - - 73.50 14.70 11.80 46.26 6.46 1.36 45.92 - 16.20 - (Zhang et al.,

2017)

1:20 150 60 - 76.50 12.60 10.90 46.69 6.40 0.90 46.02 - 16.30 -

1:20 180 60 - 76.90 11.00 12.10 49.26 6.48 0.68 43.57 - 16.50 -

1:20 210 60 - 74.80 12.40 12.80 50.34 6.31 0.57 42.78 - 17.10 -

1:20 240 60 - 63.00 21.50 15.50 54.20 6.15 0.47 39.17 - 18.10 -

Corn stalk - - - - 87.19 2.59 2.59 45.67 6.42 0.31 47.60 - 17.65 - (Wang et al.,

2018b)

1:15 160 30 - 86.10 13.44 0.46 47.38 6.12 0.19 46.31 - 18.67 -

1:15 180 30 - 85.49 13.98 0.53 49.25 6.21 0.25 44.28 - 19.47 -

1:15 200 30 - 81.97 17.36 0.68 51.61 6.10 0.44 41.84 - 20.46 -

1:15 220 30 - 79.56 19.99 0.45 53.49 6.02 0.36 40.13 - 21.17 -

Bamboo - - - - 84.78 14.35 0.92 49.55 6.69 0.35 43.41 - 17.66 - (Wang et al.,

sawdust 2018c)

32
 1:10 180 30 - 83.91 15.81 0.28 52.02 4.91 0.33 42.74 - 18.44 -

1:10 210 30 - 77.91 21.79 0.30 56.42 4.70 0.20 38.68 - 19.58 -

1:10 240 30 - 63.04 36.59 0.37 65.00 4.38 0.18 30.44 - 20.91 -

Beech - - - 8.70 78.30 12.60 0.40 49.34 5.53 0.14 44.94 0.04 17.40 - (Jian et al.,

2019)

1:20 200 10 4.60 74.20 21.00 0.20 51.11 5.69 0.19 42.97 0.03 19.10 -

Wheat straw - - - 8.50 80.00 7.80 3.70 51.25 5.18 0.63 42.81 0.13 17.10 - (Jian et al.,

2019)

1:20 200 10 4.90 81.70 12.10 1.30 53.02 5.36 0.63 40.88 0.11 19.30 -

Norway - - - - 86.50 13.27 0.23 50.31 6.24 0.07 43.38 <0.02 20.42 - (Bach et al.,

spruce 2015b)

(softwood) 1:5 175 30 - 85.72 14.17 0.11 51.34 6.18 0.07 42.42 <0.02 20.81 88.27

1:5 200 30 - 83.92 15.95 0.12 52.55 6.15 0.06 41.23 <0.02 21.33 78.45

1:5 225 30 - 74.74 25.12 0.14 56.99 5.87 0.07 37.07 <0.02 22.97 69.74

1:5 200 10 - 84.64 15.22 0.14 51.21 6.39 0.06 42.35 <0.02 21.02 82.48

1:5 200 30 - 83.92 15.95 0.12 52.55 6.15 0.06 41.23 <0.02 21.33 78.45

1:5 200 60 - 81.87 18.04 0.09 53.69 5.89 0.06 40.36 <0.02 21.51 73.28

Norway - - - - 89.46 10.26 0.28 48.94 6.35 0.11 44.60 <0.02 19.94 (Bach et al.,

birch 2015b)

(hardwood) 1:5 175 30 - 88.57 11.34 0.09 49.42 6.38 0.12 44.07 <0.02 20.21 79.53

1:5 200 30 - 85.15 14.76 0.09 51.25 6.18 0.11 42.46 <0.02 20.78 64.64

1:5 225 30 - 73.78 26.09 0.13 56.92 5.86 0.09 37.13 <0.02 22.93 58.01

1:5 200 10 - 87.97 11.94 0.08 49.61 6.16 0.13 44.10 <0.02 20.01 66.42

33
 1:5 200 30 - 85.15 14.76 0.09 51.25 6.18 0.11 42.46 <0.02 20.78 64.64

1:5 200 60 - 82.64 17.27 0.10 51.34 5.94 0.13 42.59 <0.02 20.51 63.06

OPF - - - 14.70 82.50 17.50 1.80 47.20 5.90 0.20 46.60 0.10 18.80 (Yuliansyah et

al., 2010)

1:10 200 30 7.60 79.50 20.50 1.30 53.60 5.70 0.20 40.40 0.10 20.50 58.30

1:10 240 30 6.40 70.30 29.70 1.30 58.60 5.40 0.30 35.70 0.10 23.00 52.00

1:10 270 30 5.50 54.10 45.90 1.20 69.40 4.90 0.40 25.30 0.10 26.70 42.50

1:10 300 30 5.20 51.90 48.10 1.00 71.10 4.90 0.40 23.50 0.10 27.30 38.40

1:10 330 30 5.00 47.70 52.30 0.70 73.90 4.90 0.40 20.70 0.10 29.00 36.70

1:10 350 30 5.20 45.20 54.80 0.80 75.10 4.80 0.40 19.50 0.10 29.70 35.10

OPT - - - 13.60 83.90 16.10 2.20 47.50 5.90 0.50 45.90 0.10 18.80 (Yuliansyah et

al., 2010)

1:10 200 30 7.50 83.80 16.20 1.80 51.40 5.90 0.40 42.10 0.10 19.90 67.80

1:10 240 30 6.50 73.40 26.60 1.80 57.50 5.60 0.60 36.20 0.10 22.60 56.90

1:10 270 30 5.10 54.90 45.10 2.20 69.30 5.10 0.80 24.60 0.10 27.00 41.70

1:10 300 30 4.80 51.20 48.80 2.10 71.40 5.00 0.80 22.60 0.10 28.00 38.70

1:10 330 30 4.60 47.20 52.80 1.90 73.40 4.90 1.00 20.60 0.10 29.40 36.90

1:10 350 30 4.50 45.00 55.00 2.10 75.30 4.90 1.00 18.60 0.20 29.70 35.30

PKS - - - - - - 7.92 29.25 6.34 0.23 63.10 1.09 12.24 (Nizamuddin

et al., 2015)

1:6.7 220 30 - - - 7.77 50.44 4.60 0.26 43.74 0.96 20.80 62.40

1:6.7 240 30 - - - 7.24 52.89 4.59 0.28 41.21 1.02 22.11 54.40

1:6.7 260 30 - - - 7.03 64.05 4.64 0.52 29.81 0.99 25.90 48.60

34
 1:6.7 280 30 - - - 7.01 65.94 4.79 0.53 27.71 1.03 26.74 44.80

1:6.7 290 30 - - - 6.96 68.54 4.73 0.56 25.08 1.10 26.80 43.00

EFB - - - 4.20 82.21 10.41 3.00 48.30 6.66 1.00 43.70 0.34 19.45 - (Parshetti et

al., 2013)

- 150 20 4.40 74.48 17.41 4.01 49.58 5.91 0.92 43.37 0.22 20.01 76.00

- 250 20 5.30 63.11 27.41 4.16 54.30 4.14 1.02 38.29 0.24 22.07 62.00

- 350 20 5.21 47.52 42.41 4.32 66.02 4.15 1.12 28.43 0.28 27.20 49.00

Grape - - - - 72.60 21.90 5.40 49.10 6.30 2.29 42.31 - 20.04 - (Pala et al.,

pomace 2014)

1:4 175 30 - 69.30 29.20 1.40 58.64 6.21 2.19 32.95 - 24.32 -

1:4 200 30 - 67.70 31.30 1.10 60.16 6.11 1.72 32.01 - 24.84 -

1:4 225 30 - 64.60 33.70 1.70 61.87 6.14 1.79 30.20 - 25.65 -

1:4 250 30 - 58.60 37.90 3.40 65.89 5.80 2.17 26.13 - 27.03 -

1:4 275 30 - 54.30 43.00 2.70 68.32 5.92 2.32 23.45 - 28.31 -

1:4 225 10 - 67.10 30.90 1.90 61.39 6.40 1.72 30.49 - 25.75 -

1:4 225 30 - 64.60 33.70 1.70 61.87 6.14 1.79 30.20 - 25.65 -

1:4 225 60 - 64.60 33.20 2.10 63.05 6.31 1.87 28.77 - 26.40 -

Loblolly pine - - - 3.60 83.70 12.30 0.40 50.25 5.97 0.00 43.34 - - - (Yan et al.,

2009)

1:5 200 5 1.30 87.10 12.40 0.50 54.72 6.03 0.14 39.11 - 21.11 88.70

1:5 230 5 1.30 83.80 15.80 0.40 56.05 5.94 0.09 37.92 - 22.09 70.60

1:5 260 5 1.30 73.20 26.30 0.50 72.07 4.90 0.16 22.89 - 26.55 57.00

Olive - - - 4.30 78.40 17.60 4.00 50.36 6.36 1.56 41.71 - 19.80 - (Volpe & Fiori,

35
trimmings 2017)

(including 1:4 120 30 3.50 81.00 15.40 3.60 50.62 6.44 1.66 41.27 - 20.00 -

leaves) 1:4 150 30 2.70 80.80 16.50 2.70 51.91 6.49 1.44 40.16 - 20.80 -

1:4 180 30 1.70 77.30 19.90 2.80 55.36 6.39 1.55 36.70 - 21.80 -

1:4 200 30 2.60 73.20 23.10 3.70 57.48 6.34 1.66 34.51 - 23.10 -

1:4 220 30 1.60 72.90 23.00 4.10 58.77 6.47 1.67 33.09 - 23.90 -

1:4 235 30 1.10 69.90 26.40 3.60 61.37 6.44 1.77 30.43 - 26.20 -

1:4 250 30 1.20 66.30 30.30 3.40 65.42 6.52 1.86 26.19 - 27.30 -

1:6.7 250 30 1.60 66.80 29.30 3.90 64.52 6.66 2.08 26.74 - 27.20 -

1:10.0 250 30 1.90 70.40 26.20 3.40 62.42 6.52 1.86 29.19 - 27.00 -

1:14.3 250 30 2.10 72.40 24.00 3.60 61.10 6.43 1.87 30.60 - 26.10 -

Olive pulp - - - 4.90 75.20 21.80 3.10 51.91 5.99 1.65 40.45 - 21.70 - (Volpe & Fiori,

(including 2017)

kernels) 1:4 120 30 1.30 75.40 21.50 3.20 53.72 6.40 1.45 38.43 - 22.00 -

1:4 150 30 1.50 75.10 22.00 2.90 53.20 6.29 1.44 39.07 - 22.10 -

1:4 180 30 1.50 73.50 22.60 3.90 57.66 6.57 1.56 34.20 - 23.50 -

1:4 200 30 1.30 69.20 25.80 4.90 61.16 6.53 1.68 30.63 - 24.30 -

1:4 220 30 2.00 69.30 26.90 3.80 62.43 6.66 1.77 29.14 - 25.70 -

1:4 235 30 1.40 67.00 28.90 4.10 63.64 6.48 1.78 28.11 - 26.40 -

1:4 250 30 1.80 63.10 32.40 4.60 68.17 6.70 1.99 23.14 - 28.40 -

1:6.7 250 30 2.10 63.50 31.60 4.90 67.61 6.62 2.00 23.76 - 27.40 -

1:10.0 250 30 2.30 65.00 30.70 4.30 65.73 6.58 1.78 25.91 - 27.60 -

36
 1:14.3 250 30 2.60 68.00 27.90 4.00 63.40 6.47 1.56 28.57 - 26.60 -

Eucalyptus - - - - 80.60 15.80 3.60 45.22 6.38 - 48.40 - 18.50 (Gao et al.,

bark 2016)

1:10 220 120 - 71.20 26.10 2.70 49.50 5.59 - 44.91 - 20.20 46.40

1:10 240 120 - 68.30 26.20 5.50 68.42 5.07 - 26.51 - 27.00 41.20

1:10 275 120 - 65.50 28.80 5.70 69.73 5.04 - 25.23 - 27.30 42.20

1:10 300 120 - 60.10 5.90 72.72 5.05 - 22.23 - 29.20 40.00

1:10 240 120 - 68.30 26.20 5.50 68.42 5.07 - 26.51 - 27.00 41.20

1:10 240 240 - 66.50 27.90 5.60 69.22 5.07 - 25.71 - 28.20 41.50

1:10 240 360 - 66.10 27.90 6.00 68.92 5.07 - 26.01 - 28.00 40.90

1:10 240 480 - 61.70 27.40 10.90 69.58 4.93 - 25.49 - 27.10 40.10

1:10 240 600 - 60.30 29.90 9.80 68.89 5.13 - 25.98 - 26.70 40.30

Wheat straw - - - - 75.48 20.62 3.90 46.86 5.93 0.46 46.37 0.39 17.60 - (Ma et al.,

2018)

1:10 160 60 - 80.56 16.74 2.20 48.75 5.96 0.33 44.45 0.51 18.56 79.90

1:10 180 60 - 78.47 18.61 2.93 50.79 5.94 0.43 42.56 0.28 19.07 65.20

1:10 200 60 - 74.21 20.48 5.30 54.85 6.12 0.46 38.24 0.32 20.28 61.30

1:10 220 60 - 70.83 24.77 4.41 56.85 6.11 0.51 36.23 0.29 21.44 57.30

1:10 240 60 - 62.54 34.19 3.26 62.72 5.76 0.60 30.50 0.41 23.88 49.20

Coconut - - - - 61.80 34.80 3.40 50.05 5.80 0.41 43.63 0.10 19.10 - (Nakason et

husk al., 2018)

1:10 140 240 - 59.80 39.60 0.50 51.56 6.04 0.50 41.79 0.10 20.70 -

1:10 160 240 - 56.90 42.60 0.60 54.02 5.82 0.50 39.56 0.10 21.60 -

37
 1:10 180 240 - 55.90 43.60 0.50 56.88 5.73 0.50 36.78 0.10 22.70 -

1:10 200 240 - 54.00 45.70 0.30 59.52 5.71 0.50 34.17 0.10 23.90 -

1:10 200 60 - 55.20 44.20 0.60 56.54 5.84 0.50 37.02 0.10 22.60 -

1:10 200 120 - 53.70 46.20 0.10 57.46 5.71 0.50 36.24 0.10 23.00 -

1:10 200 180 - 53.50 46.20 0.40 58.48 5.82 0.50 35.11 0.10 23.50 -

1:10 200 240 - 54.00 45.70 0.30 59.52 5.71 0.50 34.17 0.10 23.90 -

Rice husk - - - - 60.30 21.50 18.20 47.32 6.71 0.73 45.12 0.12 15.60 - (Nakason et

al., 2018)

1:10 140 240 - 56.20 23.90 19.90 48.05 6.45 0.61 44.77 0.12 16.10 -

1:10 160 240 - 52.50 26.50 21.10 50.64 6.76 0.77 41.71 0.13 16.20 -

1:10 180 240 - 51.40 27.60 21.10 53.75 6.61 0.64 38.88 0.13 17.30 -

1:10 200 240 - 48.30 30.10 21.60 56.76 6.51 0.77 35.84 0.13 18.20 -

1:10 200 60 - 51.10 28.00 20.90 54.11 6.57 0.63 38.56 0.13 17.50 -

1:10 200 120 - 49.60 29.20 21.20 54.70 6.47 0.63 38.07 0.13 17.60 -

1:10 200 180 - 49.30 29.10 21.60 55.54 6.62 0.76 36.94 0.13 17.80 -

1:10 200 240 - 48.30 30.10 21.60 56.76 6.51 0.77 35.84 0.13 18.20 -

Bamboo - - - - 92.45 6.75 0.80 49.55 6.69 0.35 43.41 - 17.66 - (Dai et al.,

sawdust 2017)

(Moso 1:10 150 30 - 90.88 8.64 0.48 50.08 6.52 0.22 43.18 - 18.35 -

bamboo) 1:10 190 30 - 89.22 10.46 0.32 51.01 6.41 0.14 42.44 - 19.89 -

1:10 230 30 - 87.90 12.02 0.08 53.42 6.23 0.12 40.22 - 20.84 -

Grape - - - 7.40 74.20 16.10 2.30 53.50 6.80 1.10 38.60 - 22.50 - (Missaoui et

pomace al., 2017)

38
1:6 215 0 1.90 72.30 25.20 0.60 62.30 7.10 1.40 29.20 - 24.90 66.00

1:6 215 5 2.60 72.90 23.50 1.00 61.20 6.80 1.50 30.50 - 25.60 70.00

1:6 215 30 3.20 70.50 25.20 1.10 64.00 7.00 1.50 27.60 - 26.80 69.00

1:6 215 60 3.30 70.20 26.00 0.50 63.30 6.80 1.30 28.50 - 26.50 66.00

1:6 215 120 1.80 68.10 28.90 1.20 65.20 6.50 1.40 26.80 - 26.20 61.00

1:6 180 30 3.70 71.60 23.60 1.10 57.80 6.70 1.60 33.90 - 24.10 71.00

1:6 200 30 1.90 70.50 27.60 <0.10 60.70 6.60 1.40 31.20 - 25.00 67.00

1:6 215 30 3.20 70.50 25.20 1.10 64.00 7.00 1.50 27.60 - 26.80 69.00

1:6 230 30 2.00 66.40 31.10 0.50 64.80 6.70 1.20 27.20 - 26.10 63.00

1:6 250 30 1.90 61.00 36.20 0.80 67.80 6.50 1.40 24.30 - 27.60 56.00

1:2 215 30 2.80 65.80 30.20 1.20 62.30 6.80 1.20 29.60 - 26.30 64.00

1:3.3 215 30 2.00 69.10 28.80 0.10 64.60 6.90 1.50 26.90 - 26.50 67.00

1:4.3 215 30 2.00 66.70 30.20 1.10 63.60 6.90 1.40 28.20 - 26.30 67.00

1:10 215 30 2.80 70.70 24.60 0.80 62.10 6.80 1.30 29.90 - 26.10 62.00

39
Catalytic wet torrefaction of lignocellulosic biomass

Introduction of catalyst in wet torrefaction and similar processes

Catalysts have been introduced into WT (Bach et al., 2015a; Nazos et al., 2020; Su et al., 2020) or

similar processes, such as HTC (Ameen et al., 2022; Lynam et al., 2011; Qi et al., 2016), hydrolysis

(Lenihan et al., 2010; Wataniyakul et al., 2018b; Zhou et al., 2013), hot compressed water

(Chareonlimkun et al., 2010a, 2010b), hydrothermal pre-treatment (Rozenfelde et al., 2021), and

high-temperature liquid water (Li et al., 2009). These processes are similar in that they all involve

the degradation of biomass or biomass components (i.e. cellulose, glucose, or xylose) in the

presence of a liquid medium, usually water. The differences between these processes are the

intensity of the reaction condition (i.e. temperature, time) or the target product. For instance,

hydrolysis usually refers to the process that aims to degrade biomass or biomass model components

into specific sugars (i.e. glucose, xylose, fructose). The reaction conditions for hydrolysis are milder

in temperature (i.e. typically 80 to 200 oC) and time (i.e. usually 5 to 120 minutes) relative to WT.

HTC has been widely used to produce carbon materials (Faradilla et al., 2021; Liang et al., 2011; Qi

et al., 2016). Nevertheless, the terms utilised are generally interchangeable, depending on target

product. In this review, the term WT will be exclusively used for the synthesis of hydrochar for

energy-driven applications.

Catalysts have also been introduced for the production of biofuel (Ameen et al., 2022; Lynam et al.,

2011; Reza et al., 2015), production of carbon-rich materials, support, and nanomaterials (Liang et

al., 2011; Qi et al., 2016; Sangjumras et al., 2018), enhancing sugar production (Lenihan et al., 2010;

Pang et al., 2010; Weerasai et al., 2018), production of solid catalysts (Laohapornchaiphan et al.,

2017; Wataniyakul et al., 2018a; Wataniyakul et al., 2018b), pre-treatment (Rozenfelde et al.,

2021; Su et al., 2020; Susanti et al., 2021), ash removal (Bach et al., 2015a), and reaction kinetics (Li

40
et al., 2009; Yat et al., 2008). In these applications, various types of catalysts were utilised, which

can be classified into two types: solid (or heterogeneous) and liquid (or homogeneous) catalysts.

Solid catalysts

Solid catalysts are also heterogeneous catalysts, which are not soluble in the water medium. Solid

catalysts can generally be sub-categorised as synthesised and commercial catalysts (Figure 2). In

terms of application, the reported solid catalyst can either be used directly (i.e. catalysts are used as

is) or sulphonated before usage. The purpose of sulphonation is to enhance the surface of the

catalysts with sulphonic functional groups (SO3H), which would increase the acidity of the

sulphonated catalysts (Weerasai et al., 2018). Acidity of catalysts was reported to play a significant

role in the acid catalytic hydrolysis of cellulose (Hara, 2010). Solid catalysts were usually utilised for

hydolysis (eucalyptus wood chips precursor (Weerasai et al., 2018), cellulose precursor (Hara,

2010)), esterification (xylose precursor (Laohapornchaiphan et al., 2017)), dehydration (xylose

precursor (Laohapornchaiphan et al., 2017)), and so forth. Synthesised catalysts in WT and HTC

applications encompass catalysts derived from glucose (Weerasai et al., 2018), defatted rice bran

(Wataniyakul et al., 2018a), water hyacinth (Laohapornchaiphan et al., 2017), sulphonated coconut

shell activated carbon, cellulose-derived carbon, and resin-derived carbon (Pang et al., 2010). On the

other hand, commercial catalysts that were studied include Amberlyst-15, Nafion SAC13, layered

niobium molybdate (HNbMoO6), HtiNbO5 nanosheets, niobic acid (Nb2O5∙nH2O) (Takagaki et al.,

2008), Amberlyst 16-wet (Wataniyakul et al., 2018a; Wataniyakul et al., 2018b), graphene oxide

(Wataniyakul et al., 2018b), sulphonated H-USY zeolite (Zhou et al., 2013), CMK-3, and acetylene

black (Pang et al., 2010).

Some researchers favoured solid catalysts to ease post-processing catalyst retrieval and eliminate

requirement for acidic liquid waste management (Takagaki et al., 2008). Solid catalysts were

generally more complex due to a multitude of factors contributing to the overall catalytic

effectiveness, such as high acidity, high tolerance to water, and facile intercalation of the component

41
within the catalyst (Takagaki et al., 2008). Some researchers reported that acidity is a key factor for

overall catalytic activities. These catalysts have high innate acidity or are modified to enhance their

acidity (Chareonlimkun et al., 2010a, 2010b; Wataniyakul et al., 2018a; Wataniyakul et al., 2018b).

Others reported that specific surface area (Pang et al., 2010; Wataniyakul et al., 2018b) or

morphology (Wataniyakul et al., 2018a) is another determining factor that affects the overall

catalytic activity of solid catalysts. Some solid catalysts were reported to be promising, given their

high acidity. Takagaki et al. (2008) suggested that the overall catalytic activity can be further

enhanced by improving the specific surface area of the catalyst. Regardless, Laohapornchaiphan et

al. (2017) reported that the contribution of morphological properties (pore volume and specific

surface area) in overall catalytic effectiveness was insignificant relative to the acidity of catalysts.

Most of the works in solid or heterogeneous catalysts have been focused onto the solid catalysts'

synthesis, modification, reusability, and recoverability. The catalytic efficiency of solid catalysts

generally depends on the combined effect of acidity, surface area or morphology of the catalyst.

Liquid catalysts

Liquid catalysts also referred to as homogeneous catalysts, are catalysts that are soluble in water.

Types of liquid catalysts that have been studied can be classified into three categories: acids, salts,

and others (Figure 2). For acids, there were mineral acid catalysts (Evcil et al., 2020; García-Bordejé

et al., 2017; Lenihan et al., 2010; Lu et al., 2009; Reiche et al., 2015; Weerasai et al., 2018; Yat et

al., 2008) (such as sulphuric acid and hydrochloric acid) and organic acid catalysts (Ameen et al.,

2022; Bach et al., 2015a; Laohapornchaiphan et al., 2017; Qi et al., 2016; Reza et al., 2015; Susanti

et al., 2019) (such as acetic acid, citric acid, ascorbic acid, formic acid, and levulinic acid). For salts,

there were chloride salts (Abd Hamid et al., 2015; Cai et al., 2016; Evcil et al., 2020; Lynam et al.,

2012; Su et al., 2020; Teh et al., 2015) (such as lithium chloride, zinc chloride, tin chloride, and

caesium chloride), sulphate salts (Ming et al., 2013; Rozenfelde et al., 2021) (such as aluminium

sulphate and sodium sulphate), and triflate salts (Simsir et al., 2019) (such as sodium triflate and

42
aluminium triflate). Lastly, the other studied catalysts were classified as others (Lynam et al., 2012)

(i.e. calcium lactate, calcium propionate, calcium formate, magnesium acetate, and etc.).

Few researchers also studied the combination of these catalysts. For instance, Lynam et al. (2011)

studied a mix of acetic acid and lithium chloride. Su et al. (2020) examined the effect of acidic

molten salts via a combined zinc chloride and acetic acid mix. The combined effect of aluminium

chloride and hydrochloric acid was studied by Evcil et al. (2020).

Factors such as water tolerance, intercalation ability, and morphology must be considered in solid

catalysts to capture the holistic catalytic effect (Takagaki et al., 2008). As the liquid catalyst is

homogeneous with the reaction media, researchers can directly evaluate the effect of liquid catalyst

addition. Further discussions are provided under Section 5, 6, and 7 that describe the differences

and similarities between each of these categories under liquid catalysts.

The effect of adding liquid catalysts onto hydrochar is generally more well-documented in the

literature than solid catalysts. Such an effect covers different target applications (i.e. enhancement

of fuel properties in WT, promotion of secondary formation in HTC, and etc.).

As mentioned, catalysts were introduced in WT or similar processes to obtain a more favourable

outcome in the process (i.e. increased heating value, enhanced sugar yield in sugar production,

increased formation of carbonaceous spheres on precursor materials, and physical and surface

properties of the hydrochar in applications). These applications are discussed in the following

subsections. Emphasis is given to the presence and concentration of catalysts added, so less

coverage is given to the effects of temperature, time, and other factors (i.e. biomass-to-liquid ratio),

as they were elucidated in previous Section 2.3. Any key observations on the formation of

carbonaceous spheres (or microsphere, carbon spheres, secondary deposits, and etc.) would also be

highlighted as elaborated in previous Section 2.3.

43
Addition of catalysts in wet torrefaction for hydrochar synthesis

Catalysts were introduced in WT to improve the hydrochar’s properties as a biofuel. Researchers

were interested in enhancing the biofuel properties of hydrochar derived from biomass, where the

effect of catalyst on yield, HHV, elemental composition, and secondary deposits was evaluated.

Acid catalysts

Acid catalysts that were studied in WT were as previously classified: mineral acids (sulphuric acid

(Nazos et al., 2020)) and organic acids (ascorbic acid (Ameen et al., 2022), citric acid (Ameen et al.,

2022; Faradilla et al., 2021), acetic acid (Lynam et al., 2011; Reza et al., 2015)). The discussion and

comparison were made based on these categories in Section 4.1.1 and 4.1.2.

Mineral acids

Nazos et al. (2020) studied the effect of adding sulphuric acid catalyst on the WT of barley straw at

200 oC and 20 minutes on the hydrochar yield and HHV. When sulphuric acid catalyst concentration

was increased from 0.010 to 0.035 M, the yield decreased from 47.5 to 31.6 wt. % while the heating

value increased from 23.44 to 24.27 MJ kg-1, attributed to enhanced barley straw degradation and

lignin densification. The carbon content increased from 45.53 to 52.51 wt. % for carbon, whilst

hydrogen remained relatively unchanged (i.e. from 5.50 to 5.79 wt. %) for raw barley straw to its

catalysed hydrochar, respectively. Unlike carbon and hydrogen, the oxygen content decreased when

wet torrefied in the presence of catalyst, from 47.86 to 40.71 wt. % could be attributed to catalyst

enhanced deoxygenation (Ameen et al., 2022). Thus, the presence of catalyst in the WT of barley

straw increased the HHV of the hydrochar and increased the carbon and hydrogen content while

decreasing the oxygen content of the hydrochar.

Organic acids

Ameen et al. (2022) studied the effect of citric and ascorbic acid on the WT of oil palm biomass (i.e.

palm kernel shell, oil palm frond, and oil palm leaves) for fuel application. At 180 oC and 30 minutes,

44
the HHV of the hydrochar derived from palm kernel shell were higher in the presence of the catalyst

when compared to the baseline (18.4 MJ kg-1). In the presence of citric and ascorbic acid, the heating

values of the hydrochar were 19.2 and 19.5 MJ kg-1, respectively. It was also reported that the yield

of hydrochar with catalysts was higher than the baseline (72.4 wt. %), at 88.7 and 87.3 wt. % in the

presence of citric and ascorbic acid, respectively. They reported that dehydration and deoxygenation

reactions were promoted in the addition of catalysts, hence producing hydrochars high in carbon

content.

Faradilla et al. (2021) studied the effect of citric acid in the WT of soybean hulls at 250 oC at 0.5, 3.0,

and 6.0 hours. They found that the presence of citric acid (around 11.0 wt. %) increased the

estimated HHV of the hydrochar (i.e. 23.5 to 26.7 MJ kg-1 at 0.5 hours, 24.1 to 26.9 MJ kg-1 at 3.0

hours, 26.5 to 29.3 MJ kg-1 at 6.0 hours). Apart from this, carbon content was reported to be

generally high (i.e. 69.2 to 74.8 wt. % at 6 hours). The yield increased significantly in the presence of

citric acid (i.e. 15.4 to 46.4 wt. % at 0.5 hours, 14.0 to 42.9 wt. % at 3.0 hours, 16.2 to 49.6 wt. % at

6.0 hours). The low mass yield for hydrochar was due to the low lignin content of soybean hulls (5.96

wt. %). The significant enhancement in yield due to the addition of citric acid was attributed to the

formation of carbonaceous deposits on the hydrochar. They stated that the formation of the carbon

spheres was linked with the catalyst-enhanced hydrolysis of cellulose into simple sugars (i.e. glucose,

fructose). This can be supported by findings reported by Qi et al. (2016), where these simple sugars

would then degrade into HMF, which would then polymerise onto the hydrochar. At 250 oC and 6

hours, the addition of citric acid catalyst increased the carbon content from 69.2 to 74.8 wt. %. At

the same time, oxygen content decreased from 22.36 to 17.86 wt. %, whilst hydrogen content

remained relatively unchanged. When compared to the addition of citric acid under a different type

of precursor (i.e. palm kernel shell (Ameen et al., 2022)), the increment in yield was relatively lower

than that reported by Faradilla et al. (2021) for soybean hulls. This disparity could be attributed to

the higher cellulose content of soybean hulls (66.71 wt. %) than palm kernel shell (44.50 wt. %). As

45
explained, secondary depositions were associated with degradation of cellulose. Hence, a significant

enhancement in yield was observed in soybean hulls but not in palm kernel shell.

Reza et al. (2015) studied the effect of varying liquid pH from 2 to 12 by adding acetic acid and

potassium hydroxide into the HTC of wheat straw at 200 and 260 oC at 6 hours reaction time. They

estimated the HHV of the biomass and hydrochar via the Boie correlation. At 200 oC and 6 hours and

a liquid pH of 7, the yield of hydrochar was reported to be 53.5 wt. % with an HHV of 21.0 MJ kg-1. As

a comparison, an HHV of raw wheat was estimated to be 20.0 MJ kg-1. With liquid pH of 2 (with

acetic acid), the yield and HHV reported were 49.9 wt. % and 21.9 MJ kg-1, respectively, where the

yield was lower and HHV was higher than the hydrochar obtained at initial liquid pH of 7. On the

other hand, when the pH of water was increased to 12 (with potassium hydroxide), the yield and

HHV were 54.1 wt. % and 20.5 MJ kg-1, respectively where it had an opposite trend to its acidic

counterpart; its yield was higher while HHV was lower instead. This was attributed to the promoted

degradation of cellulose and hemicellulose only in acidic region (i.e. pH 2) and lignin only in basic

region (i.e. pH 12). In the analysis of components in their respective process liquid after the HTC,

liquid with initial pH of 2 had the highest HMF and furfural concentration, at 805 and 1076.71 mg L-1,

respectively. The HMF and furfural concentrations at initial liquid pH 7 and 12 were 403 and 732 mg

L-1, and 568 and 282 mg L-1, respectively. HMF came from the degradation of cellulose, whereas

furfural came from the degradation of hemicellulose (and possibly cellulose). Higher concentration

of HMF indicates an increased degradation rate in the acidic region. This statement is supported by

the reported lignocellulosic content analysis, where hydrochar from initial liquid pH of 2 had a

cellulose content of 35.35 wt. %, whereas the one from initial liquid pH of 7 was 43.25 wt. %,

indicating an increased degradation of cellulose due to decreased pH (the presence of acetic acid).

Similar trend in cellulose could be observed when the HTC temperature was increased from 200 to

260 oC (i.e. cellulose content of 4.28 to 7.24 wt. % at an initial liquid pH of 2 to 7 at 260 oC,

respectively). Nevertheless, HMF was absent in the process liquid at 260 oC, possibly due to its

participation in polymerisation of components to form carbonaceous deposits (Cai et al., 2016; Qi et

46
al., 2016) or degradation into subsequent components (i.e. levulinic and formic acid (Qi et al.,

2016)).

Lynam et al. (2011) studied the HTC of loblolly pine with acetic acid as the catalyst to determine its

effect on the hydrochar based on their fuel properties. At 230 oC and 5 minutes, addition of acetic

acid decreased the yield of hydrochar (i.e. 75 wt. % for baseline, 72 wt. % for 0.4 g acetic acid per g

pine), while its heating value was increased (i.e. 21.01 MJ kg-1 for baseline, 22.16 MJ kg-1 for 0.4 g

acetic acid per g pine). When the amount of catalyst was increased, mixed results were reported, i.e.

at increment of acetic acid (i.e. 0.2 to 0.6 g acetic acid per g pine), the yield decreased (i.e. 72 to 71

wt. %), and HHV increased (21.79 to 22.06 MJ kg-1 at 0.2 to 0.6 g acetic acid per g pine). However,

when the amount of catalyst was further increased (from 0.6 to 0.8 g acetic acid per g pine), the HHV

decreased from 22.06 to 21.52 MJ kg-1. The reduction in yield was similar as previously, from 71 to

70 wt. %. Hydrochar with the highest HHV was obtained at 0.4 g acetic acid per g pine. There is no

increment in yield noticed with increasing acetic acid amount. The reduction in yield and increment

in HHV could be attributed to the degradation of cellulose and hemicellulose and the densification of

lignin. Hence, based on the works of Reza et al. (2015) and Lynam et al. (2011), the addition of

organic acid catalyst, specifically acetic acid, does not necessarily have a positive effect on hydrochar

mass yield.

Generally, in the presence of mineral acid and organic acid, a positive effect was reported for HHV,

while varying results were reported for the effect on yield (both increase and decrease were

observed). Interestingly, addition of organic acids (i.e. citric, ascorbic) was reported to enhance yield,

though not all were favourable (i.e. acetic acid was reported to give lower yield). Both of these

effects on yield were plausible, as the increase in yield could be associated with the formation of

secondary deposits, whilst a reduction in yield could be attributed to enhanced degradation of

cellulose and hemicellulose. It is also very dependent on the types of biomass used as well. The

effect of acid catalysts was also more prominent, especially towards fuel properties, as Reza et al.

47
(2015) demonstrated. Addition of both mineral and organic catalysts led to carbon-rich hydrochar as

well, as deoxygenation was reported to be the dominant reaction, with dehydration as the second

dominant reaction. Promotion of carbon spheres formation was also reported consistently. Results

reported on the concentration of HMF in the liquid medium also supported the finding that HMF

was polymerised onto the solid hydrochar in the form of secondary deposits (or carbon spheres) (Qi

et al., 2016).

Salt catalysts

Salt catalysts that were studied in WT were as previously classified: chloride salts (calcium chloride

(Hasan et al., 2021; Lynam et al., 2012), caesium chloride (Hasan et al., 2021), lithium chloride

(Lynam et al., 2011; Lynam et al., 2012), tin chloride (Hasan et al., 2021), zinc chloride (Hasan et al.,

2021)), and triflate salts (aluminium triflate and sodium triflate (Simsir et al., 2019)). The discussion

and comparison were made based on these categories in Sections 4.2.1. and 4.2.2.

Chloride salts

Hasan et al. (2021) studied the effect of chloride catalysts (i.e. tin chloride (SnCl2), caesium chloride

(CsCl), zinc chloride (ZnCl2)) on the WT of grapeseed. In the baseline study of different temperatures

(i.e. 200 to 250 oC) and time (6 to 24 hours). When chloride salts were added, their effects on

hydrochar were favourable, where yield, HHV, and carbon content increased, while hydrogen and

oxygen content decreased when compared to its non-catalytic counterpart. For instance, at 250 oC

and 12 hours, when 0.2 M of SnCl2 was present, the yield increased from 53.78 to 64.93 wt. %, HHV

increased from 24.28 to 27.69 MJ kg-1, carbon content increased from 61.45 to 69.64 wt. %,

hydrogen decreased from 6.21 to 5.88 wt. %, and oxygen decreased from 30.08 to 23.85 wt. %.

Similar trends were observed when 0.2 M of CsCl and ZnCl2 were added separately, although not as

high as SnCl2 (i.e. 55.1 and 57.1 to 64.93 wt. % yield, 26.88 and 26.80 to 27.69 MJ kg-1 for SnCl2, CsCl,

and ZnCl2, respectively). Also, from the SEM results of the hydrochar obtained from these catalysts,

it was observed that the hydrochar obtained from the HTC of grapeseed in the presence of SnCl2 had

48
clumped nanospheres, while hydrochar from CsCl and ZnCl2 as well as the non-catalytic runs

contains microspheres on the surface.

Apart from acetic acid, Lynam et al. (2011) also studied the HTC of loblolly pine with lithium chloride

at similar parameters (230 oC and 5 minutes). Similar to acetic acid, addition of LiCl also decreased

the yield (75 wt. % for baseline, 65 wt. % for 1 g LiCl per g pine) and increased HHV of hydrochar

(21.01 MJ kg-1 for baseline, 24. 61 MJ kg-1 for 1g LiCl per g pine). When the amount of LiCl was

increased from 1 to 2 g LiCl per g pine, the mass yield (i.e. 65 to 66 wt. %) and HHV (i.e. 24.61 to 25.

41 MJ kg-1) were enhanced. Hence LiCl catalyst enhanced the HHV and yield of the loblolly pine

hydrochar, where enhancement in yield could be due to secondary deposits (Hasan et al., 2021). In

another work, Lynam et al. (2012) also studied the addition of calcium chloride and lithium chloride

in the WT of loblolly pine at 260 oC and 5 minutes. The yield and HHV in the presence of calcium

chloride and lithium chloride were both higher when compared to the baseline, at yield of 61.4,

60.9, 59.9 wt. %, and HHV of 27.51, 28.20, 25.11 MJ kg-1, respectively.

Therefore, chloride salts were generally reported to have favourable results, similar to some organic

acids (citric and ascorbic acid). The enhancement in HHV could be attributed to the enhanced

degradation of celluloses and hemicelluloses in the lignocellulosic biomass, which led to the

densification of lignin composition, as well as the formation of secondary deposits. Deposition of

products on the hydrochar during WT (and even HTC) was also observed. HMF is one of the key

components in the formation of deposited products (or carbon spheres) on the hydrochar (Cai et al.,

2016; Liang et al., 2011; Qi et al., 2016), where it was reported to have an HHV of approximately

22.05 MJ kg-1 (O'Neill, 2006) to 22.06 MJ kg-1 (Kambo & Dutta, 2015). This HHV was relatively higher

than the HHV of cellulose and hemicellulose (i.e. approximately 18.60 MJ kg-1 for cellulose and

hemicellulose (Demirbaş, 2001)).

49
Triflate salts

Simsir et al. (2019) studied the WT of glucose and cellulose in the presence of acidic and alkaline

metal triflates (i.e. NaOTf, Al(OTf)3) based on its yield, HHV, and elemental composition (i.e. C, H, O).

When 0.05 M NaOTf was added into the HTC of glucose at 200 oC and 48 hours and compared to its

non-catalytic counterpart, the yield increased from 43.10 to 48.00 wt. %, while the HHV slightly

decreased from 25.05 to 24.51 MJ kg-1. When the catalyst amount was increased to 0.20 M, the yield

became lower (i.e. 44.67 wt. %) but had increased HHV (i.e. 26.44 MJ kg-1. When 0.05 M of Al(OTf)3

was added into the HTC of glucose, the yield was drastically lower (i.e. 31.33 wt. %) and had a

slightly higher HHV (i.e. 25.48 MJ kg-1) when compared to the non-catalytic run (43.10 wt. % yield

and 25.05 MJ kg-1 HHV). Similar trends were identified when the catalyst amount was increased to

0.20 M, where the yield had decreased to 28.00 wt. % and HHV had increased to 26.64 MJ kg-1. The

only noticeable difference was the yield of hydrochar from the two different catalysts, while HHV

remained relatively close, with Al(OTf)3 catalysed hydrochar having slightly higher HHV. On the other

hand, when the catalyst was used on the HTC of cellulose instead at the same parameter (200 oC, 48

hours), a similar trend in yield was identified with NaoTf (i.e. 44.67 to 55.33 to 52.67 wt. % for non-

catalytic, 1 and 0.2 M of NaOTf) and Al(OTf)3 (i.e. 44.67 to 38.67 to 36 wt. % for non-catalytic, 1 and

0.2 M of Al(OTf)3). However, the HHVs of hydrochar catalysed by NaOTf were all lower than their

non-catalytic counterpart (i.e. 22.51 to 24.38 MJ kg-1 for 0.20 M catalyst to non-catalytic). On the

other hand, the HHV of hydrochar catalysed by Al(OTf)3 retained the same trend as the HTC of

glucose (i.e. 26.2 to 24.38 MJ kg-1 for 0.2 M catalyst to non-catalytic). They explained that NaOTf

inhibited the process. Al(OTf)3 was also observed to promote the formation of secondary deposits in

their presence. Hence, triflate salts were reported to exhibit results without a consistent trend, as

0.05 M of NaOtf was reported to have ‘hindered’ the WT process, such that hydrochar had higher

yield and lower HHV. The inhibition seemed lower when the catalysts concentration increased,

where reported yield and HHV were higher, but the HHV was still lower than its precursor material.

Regardless, this indicated the importance of understanding the correlation between catalyst

50
concentration and the quality of produced hydrochar. On the other hand, Al(OTf)3 was reported to

give a result similar to that of mineral acid catalysts. In exchange, accelerated degradation caused

the yield to be lower but enhanced its HHV.

Others

In this category, catalysts that were studied that do not fall into the assigned group would be

classified as others, which include calcium lactate (Lynam et al., 2012), calcium propionate (Lynam

et al., 2012), calcium acetate (Lynam et al., 2012), calcium formate (Lynam et al., 2012), magnesium

acetate (Lynam et al., 2012), zinc chloride and acetic acid mixture (Su et al., 2020), and lithium

chloride and acetic mixture (Lynam et al., 2011).

Lynam et al. (2012) studied the WT of loblolly pine in the presence of various catalysts (i.e. calcium

lactate, calcium propionate, calcium acetate, calcium formate, magnesium acetate) at 260 oC and 5

minutes of WT time and reported the respective yields and HHV. It was found that calcium formate

catalysed WT had a higher yield and lowered HHV when compared to the non-catalytic hydrochar, at

72.8 to 59.9 wt. % and 21.47 to 25.11 MJ kg-1, respectively. They described that the presence of

calcium formate as a catalyst hindered cellulose and hemicellulose degradation during the HTC,

hence the higher yield and lower HHV. Then, calcium propionate, calcium acetate, and magnesium

acetate were found to be fairly neutral regarding yield and HHV compared to the non-catalytic HTC,

at 62.8, 58.3, 51.7 and 59.9 wt. % and 24.90, 25.34, 25.88, and 25.11 MJ kg-1, respectively. On the

other hand, calcium lactate was found to increase the HHV of hydrochar compared to the non-

catalytic one, at 26.94 to 25.11 MJ kg-1, respectively. For yield, reduction was observed, at 55.3 to

59.9 wt. %, respectively. The lower yield and higher HHV were associated with the increased

degradation of cellulose and hemicellulose, leaving the hydrochar mainly consisting of lignin, hence

lower yield and higher heating value. The higher yield and HHV were attributed to the potential

formation of products with high HHV for calcium chloride and lithium chloride. Both postulations are

possible, as lignin tends to have a higher HHV than those of cellulose and hemicellulose (i.e.

51
approximately 23.26 to 25.58 MJ kg-1 for lignin, 18.60 MJ kg-1 for cellulose and hemicellulose

(Demirbaş, 2001)). To support this postulation, a lignocellulosic composition analysis could be

performed (Reza et al., 2015). A hydrochar with higher lignin percentage would be expected to have

a higher HHV than a hydrochar with residual celluloses or hemicelluloses.

Su et al. (2020) reported the fuel properties of the hydrochar obtained from the WT of rice husk for

the purpose of pre-treatment prior to pyrolysis. At 120 oC and 4 hours, the presence of 20 wt. %

acidic molten salt (ZnCl2 hydrated with acetic acid at 1:1 weight ratio) increased the yield of

hydrochar when compared to the yield without catalyst (i.e. 79.37 and 78.21 wt. % respectively)

while the HHV of hydrochar decreased (i.e. 16.53 and 16.77, respectively). This result generally

contradicts the reported behaviour of catalysts (particularly, acidic catalysts) where acid catalysts

tend to enhance the HHV of hydrochar, at the cost of reduced yield. The addition of catalyst

increased the carbon content slightly, from 45.45 to 46.1 wt. %, hydrogen content from 5.75 to 6.09

wt. %, and decreased oxygen content from 34.88 to 33.16 wt. % when compared to the hydrochar

from WT without catalyst. Su et al. (2020) reported that the catalysed hydrochar had higher carbon

content, though no further correlation was provided on its relationship to its HHV.

Aside from studying acetic acid and lithium chloride as catalysts independently, Lynam et al. (2011)

also studied the effect of both catalysts mixed (1 g LiCl and 0.4 g acetic acid per g pine) on the HTC of

loblolly pine at the same parameter (230 oC and 5 minutes). With this mixture, a lower yield was

reported (57 wt. %) when compared to baseline (75 wt. %) and independent catalysts study (65 and

72 wt. % for 1 g and 0.4 g LiCl and acetic acid per g pine, respectively), but its respective HHV was

reported to be the highest (i.e. 26.72 MJ kg-1 for combined catalyst, 21.01 MJ kg-1 for baseline, 24. 61

MJ kg-1 for 1 g LiCl per g pine, and 22.16 MJ kg-1 for 0.4 g acetic acid per g pine). They contributed to

hydrochar with lower yield and higher HHV and could be attributed to the additive catalytic effect.

Mixed catalysts would benefit greatly from more research and fundamental studies to better

understand the synergy of different catalyst combinations, as they may not necessarily be beneficial.

52
For instance, Evcil et al. (2020) studied the effect of catalyst mixture of 0.3 M aluminium chloride

and 0.3 M hydrochloric acid in the HTC of fir wood between 225 to 275 oC for 6 to 24 hours. With the

addition of catalyst (0.3 M aluminium chloride and 0.3 M hydrochloric acid), it was reported that

both the yield and HHV of hydrochar reduced (i.e. at 275 oC and 12 hours, yield reduced from 38.22

to 36.26 wt. % and HHV reduced from 29.09 to 27.44 MJ kg-1, without and with catalyst,

respectively). The reduction in yield was attributed to the promoted degradation of cellulose and

hemicellulose from acid by encouraging C-O and C-C bonds in the lignocellulosic component to

crack. Nevertheless, there was no explanation given in light of the contradicting finding of the

reduced HHV due to the effect of the catalyst. Individual additions of organic acid (acetic acid)

catalyst and chloride salt (aluminium chloride) catalyst were reported to enhance HHV of hydrochar.

However, a combination of these catalysts was reported to decrease the HHV of the hydrochar. To

this end, more research and studies on the fundamental level of catalyst combinations are

warranted.

In the addition of catalyst in WT or HTC of biomass for fuel purposes, most researchers reported that

catalyst addition increased the HHV of hydrochar produced when compared to its non-catalytic

counterpart (Ameen et al., 2022; Hasan et al., 2021; Lynam et al., 2011; Lynam et al., 2012; Nazos

et al., 2020; Reza et al., 2015; Simsir et al., 2019), though some findings observed a reduction

instead (Evcil et al., 2020; Su et al., 2020). In some cases, catalysts addition was also observed to be

insignificant, suggesting the absence of catalytic behaviour (Lynam et al., 2012). Formation of

carbon spheres deposited onto the hydrochar were also observed (Ameen et al., 2022; Evcil et al.,

2020; Faradilla et al., 2021; Hasan et al., 2021; Simsir et al., 2019). For yield, mineral acid catalysts

and selected triflate salt (e.g. Al(OTf)3) and lactate salt (e.g., calcium lactate) reported a reduced

yield in their presence, while organic acid catalysts and chloride salts reported an increased yield.

Carbon content was generally reported to increase in the presence of catalyst, while oxygen content

generally decreased with negligible changes for hydrogen. Yield of hydrochar also varied from one

finding to another (i.e. some reported addition of catalyst to increase yield and vice versa).

53
Concentration of catalyst was also observed to have a positive correlation with hydrochar’s HHV,

though the yield may vary. Therefore, based on the studies reviewed, an increment in HHV has been

strongly related to higher carbon content and carbon sphere formation. Table 4 summarises the

results of the studies on catalytic WT and HTC for fuel application.

54
 Table 4. Compilation of results from studies on catalytic WT and HTC for fuel application.

Precursor Biomass- Catalyst Catalyst Temperature Time Yield ( HHV Elemental composition (wt. %) Carbon spheres Ref
o
to-liquid- concentration ( C) %) (MJ formation
C H N S O
mass ratio
-1
kg )

Cellulose 1.5: 20 - - 200 48 hr 44.70 24.40 67.00 4.70 - - 28.20 - (Simsir

et al.,
NaOTf 0.05 M 55.30 20.30 56.00 5.70 - - 38.30 Inhibited
2019)
formation
0.10 M 54.00 21.20 57.90 5.70 - - 36.40

0.20 M 52.70 22.50 61.60 5.30 - - 33.10

Al(OTf)3 0.05 M 38.70 25.60 66.70 5.60 - - 27.70 Irregular

formation
0.10 M 38.00 25.40 66.80 5.40 - - 27.80

0.20 M 36.00 26.20 67.60 5.70 - -

Glucose 1.5:20 - - 200 48 hr 43.10 25.10 68.50 4.70 - - 26.80 -

NaOTf 0.05 M 48.00 24.50 66.30 5.10 - - 28.60 Inhibited

55
 0.10 M 47.30 25.30 67.60 5.10 - - 27.30 formation

0.20 M 44.70 26.40 68.90 5.40 - - 25.70

Al(OTf)3 0.05 M 31.30 25.50 66.70 5.50 - - 27.80 Irregular

formation
0.10 M 30.00 26.10 67.60 5.60 - - 26.80

0.20 M 28.00 26.60 68.90 5.60 - - 25.60

Barley - H2SO4 0.010 M 200 20 min 47.50 23.40 - - - - - - (Nazos

straw et al.,
0.035 M 31.60 24.30 - - - - - -
2020)

Fir wood 1:20 - - 275 12 hr 38.20 29.10 73.70 5.10 0.40 - 20.80 - (Evcil et

al.,
AlCl3 and 0.30 M AlCl3, 36.30 27.40 74.30 4.90 0.11 - 20.70 Irregular
2020)
HCl formation
0.30 M HCl
mixture

Grapeseed 1:10 - - 250 12 hr 53.70 24.30 61.50 6.20 2.20 0.10 30.10 Microspheres (Hasan

et al.,

56
 formation 2021)

CsCl 0.20 M 250 12 hr 55.10 26.90 63.50 7.20 1.60 0.10 27.60

ZnCl2 250 12 hr 57.10 26.80 66.00 6.40 1.40 0.10 26.10

SnCl2 250 12 hr 64.90 27.70 69.60 5.90 0.50 0.10 23.90 Agglomerated

sphere

formation

Loblolly 1:5 - - 230 5 min 75.00 21.00 - - - - - - (Lynam

pine et al.,
LiCl 1 g per g 65.00 24.60 - - - - - -
2011)
precursor

2 g per g 66.00 25.40 - - - - - -

precursor

CH3COOH 0.2 g per g 74.00 21.80 - - - - - -

(Acetic precursor

acid)
0.4 g per g 72.00 22.20 - - - - - -

57
 precursor

0.6 g per g 71.00 22.10 - - - - - -

precursor

0.8 g per g 70.00 21.50 - - - - - -

precursor

LiCl and 1g LiCl and 0.4 57.00 26.70 - - - - - -

CH3COOH g CH3COOH

(Acetic per g

acid) precursor

- - 260 59.90 25.10 - - - - - - (Lynam

et al.,
C6H10CaO6 1 g per g 55.30 26.90 - - - - - -
2012)
precursor
(Calcium

lactate)

CaCl2 61.40 27.50 - - - - - -

58
 LiCl 60.90 28.20 - - - - - -

C6H10CaO4 62.80 24.90 - - - - - -

(Calcium

propionate

C4H6CaO4 58.30 25.30 - - - - - -

(Calcium

acetate)

Ca(HCOO)2 72.80 21.50 - - - - - -

(Calcium

formate)

Mg(CH3CO 51.70 25.90 - - - - - -

O)2

(Magnesiu

59
 m acetate)

Palm 1:10 - - 180 30 min 72.40 18.40 44.50 6.10 5.10 - 43.00 - (Ameen

kernel shell et al.,

C6H8O7 10 wt. % 88.70 19.20 48.60 6.10 3.40 - 41.60 Microsphere
2022)
solution formation
(Citric acid)

C6H8O6 10 wt. % 87.30 19.50 49.20 6.20 3.30 - 41.10

solution
(Ascorbic

acid)

Rice husks 1:10 - - 120 4 hr 78.20 16.80 45.50 5.80 0.40 - 34.90 Observed (Su et

al.,
CH3COOH 10 wt. % 120 4 hr 79.40 16.50 46.10 6.10 0.40 - 33.20 Observed
2020)
(Acetic solution

acid) and CH3COOH and

ZnCl2 10 wt. %

solution ZnCl2

Soybean 1:09 - - 250 6 hr 16.20 26.50 69.20 5.00 3.50 - 22.40 - (Faradill

60
hulls C6H8O7 11 wt. % 49.60 29.30 74.80 5.00 2.30 - 17.90 Porous flaky a et al.,

solution deposits 2021)

(Citric acid)

Wheat 1:20 CH3COOH - (pH 2) 260 6 hr 31.30 26.20 66.00 4.20 0.80 0.20 16.90 - (Reza et

straw (Acetic al.,

- (pH 3) 34.40 27.10 65.70 5.00 1.10 0.40 17.40 -
acid) 2015)

- (pH 4) 32.60 26.40 64.40 4.90 1.20 0.30 18.30 -

- (pH 5) 35.30 26.20 63.90 4.90 1.10 0.30 18.40 -

- (pH 6) 35.90 26.30 64.30 4.80 1.10 0.30 18.00 -

- - (pH 7) 35.70 26.20 64.20 4.80 1.10 0.30 18.80 -

KOH - (pH 8) 34.90 26.50 64.80 4.90 1.10 0.30 17.70 -

- (pH 9) 34.60 26.10 64.10 4.80 1.10 0.30 18.80 -

- (pH 10) 34.20 26.70 64.60 5.00 1.10 0.30 17.30 -

- (pH 11) 34.30 26.50 64.30 4.90 1.10 0.20 17.50 -

61
- (pH 12) 34.40 26.50 64.00 5.00 1.10 0.30 16.90 -

62
Addition of catalysts in hydrothermal carbonisation for carbon materials synthesis

In the addition of catalyst in HTC of biomass or biomass components, researchers were primarily

interested in the effect of catalyst in promoting secondary formation onto primary hydrochar

obtained in the process. Some researchers analysed the building blocks of these carbonaceous

deposits and their respective diameters to understand the correlation between catalyst addition and

the rate of secondary formation. They are primarily interested in manipulating the size of these

spherical formations to synthesise hydrochar with favourable morphology.

Acid catalysts

Acid catalysts that were studied in HTC were as previously classified: mineral acids (hydrochloric acid

(García-Bordejé et al., 2017), nitric acid (Reiche et al., 2015)) and organic acids (levulinic acid (Qi et

al., 2016), formic acid (Laohapornchaiphan et al., 2017; Qi et al., 2016)). The discussion and

comparison were based on these categories in Sections 5.1.1 and 5.1.2.

Mineral acids

García-Bordejé et al. (2017) studied the effect of hydrochloric acid using varied concentrations

between 2 and 5 M on the HTC of micro-crystalline cellulose (MCC) at two different temperatures

(195 and 215 oC) and times (20 and 40 hours). At 20 hours, when HTC temperature increased from

195 to 215 oC, the yield decreased from 32.3 to 30.5 wt. %, carbon content increased from 68.3 to 70

wt. %, hydrogen remained similar at 4.5 wt. %, oxygen decreased from 27.1 to 25.3 wt. %, and

average carbon sphere sizes increased from 120 to 180 microns. The effect of reaction time (20 and

40 hours) was more interesting across these characteristics. For instance, at 195 oC, when the

reaction time was increased from 20 to 40 hours, the yield of hydrochar increased from 32.3 to 41

wt. %, whilst elemental composition remained relatively similar (i.e. 68.3 to 67.8 wt. % carbon, 4.5 to

4.3 wt. % hydrogen, 27.1 to 27.6 wt. % oxygen at 20 to 40 hours, respectively). On the other hand,

the average diameter of particles deposited reduced significantly, from 120 to 40 microns, when the

63
reaction time increased from 20 to 40 hours at 195 oC. Similar trends were also observed at 215 oC

for the properties. Apart from temperature and pressure, the addition of acid also affected the

properties of hydrochar significantly. For instance, at 215 oC and 40 hours, when 2 M HCl was added,

the yield of hydrochar dropped significantly, from 42.2 to 21 wt. %. The carbon content increased

from 69.7 to 77.2 wt. %, hydrogen content increased from 4.5 to 5.7 wt. %, while oxygen decreased

from 25.6 to 17.1 wt. %. This suggested that the addition of HCl promoted deoxygenation and

hydrolysis and the average diameter formed rapidly increased from 50 to 600 microns. When the

concentration of HCl was increased from 2 to 5 M at the same parameter (150 oC, 40 hours), the

hydrochar yield increased from 21 to 26.6 wt. %, carbon content increased from 77.2 to 81.1 wt. %,

hydrogen content increased from 5.7 to 6 wt. %, oxygen content decreased from 17.1 to 12.8 wt. %,

and average particle diameter decreased from 600 to 280 microns. In short, the addition of HCl

caused a reduction in the hydrochar yield and hydrogen content, while increasing the carbon

content, oxygen content, and average particle diameter. However, when HCl concentration was

increased from 2 to 5 M, an increase in hydrochar yield and a decrease in average particle diameter

were observed, whilst the trend on elemental composition remained similar (i.e. increased carbon

and hydrogen content, decreased oxygen content).

The increase in diameter due to the addition of 2 M HCl was attributed to the reaction mechanism

(Figure 5), which is referred to as the hydrothermal pathways, where the presence of catalyst

promoted the soluble pathway. Due to the promoted polymerisation, carbon spheres of larger sizes

were formed. The reduction in yield of hydrochar, on the other hand, could be attributed to the

promoted degradation of the MCC. The increase in yield when concentration of HCl was increased

could also be explained by the deduced reaction mechanism, where the ‘soluble pathway’ was the

dominant reaction. In this pathway, precursors derived from glucose would polymerise onto the

initial hydrothermal carbon, hence the formation of carbonaceous deposits onto the existing solid.

This was also supported by the increased carbon content on the hydrochar. The reduction in average

particle size observed when HCl concentration was increased could be attributed to the further

64
degradation of the glucose-degradation product (i.e. HMF into levulinic acid), where levulinic acid

then partakes in the polymerisation (Qi et al., 2016).

Figure 5. The two hydrothermal pathways for conversion of cellulose to carbon materials

(reproduced from García-Bordejé et al. (2017)).

Reiche et al. (2015) reported that when the concentration of nitric acid (HNO3) was manipulated in

the form of solution pH on the HTC of glucose at 220 oC and 6 hours when the pH decreased from 6

to 3, a significant increase in carbonaceous sphere size was identified (from approximately 500 nm

to 1 micron). When the concentration of HNO3 increased, the size of carbon spheres deposited

increased. When the concentration was increased (from pH of 3 to pH of 1), the carbon sphere size

further increased from 1 micron to a range of 4 to 15 microns, and noticeably more deformed. A

general trend of increasing carbon content in the hydrochar was identified when HNO3

concentration was increased (i.e. 68.6 wt. % at pH 3 to 69.6 wt. % at pH 1). Other elemental

compositions remained relatively similar. A similar observation was reported in the presence of

mineral acid catalysts such as hydrochloric acid (García-Bordejé et al., 2017) and nitric acid.

65
Increased catalyst concentration led to secondary deposits that were more deformed and larger in

particle size. Hence, it can be concluded that the presence of these mineral acid catalysts would lead

to enhanced secondary depositions (Qi et al., 2016).

Organic acids

In the HTC of sucrose in the presence of levulinic and formic acid at 180 oC between 3 to 6 hours, Qi

et al. (2016) reported some interesting results regarding the formation of carbonaceous spheres

(Figure 6). They studied the HTC of sucrose without any catalyst as a baseline between 3 to 6 hours

at 180 oC and reported that the average diameter of carbonaceous spheres formed was

approximately 157 nm at 3 hours and increased to 288 nm at 6 hours of duration, which indicates

that the size of the carbon spheres produced increased as carbonisation time increased. They then

added 0.1 M of levulinic acid and found that the average diameter of the carbon spheres was slightly

larger than the baseline at 3 hours (157 to 177 nm) and 6 hours (288 to 470 nm). Subsequently, in

the addition of formic acid at 0.159 M, a drastic increase in the average diameter of the

carbonaceous spheres was identified against the baseline at 3 hours (157 to 538 nm) and 6 hours

(288 to 1116 nm). These observations support that the presence of catalyst (levulinic and formic

acid) can promote the formation of these carbonaceous spheres. For instance, Figure 7 shows the

SEM images of the hydrochar from 3 to 6 hours in the presence of the mixed acid system, and it can

be observed that as reaction time increased, the carbon spheres formed also increased in size

(Figure 7(a) to Figure 7(i)) with slight deformation when reaction time approached 6 hours (Figure

7(i)).

66
Figure 6. Values of diameter obtained from various systems across reaction time (reproduced from

Qi et al. (2016)).

67
 Figure 7. SEM result of hydrochar obtained from the HTC of sucrose (0.1 M) in the mixed system of

formic acid (0.05 M) and levulinic acid (0.1 M) for the duration of (a) 3 hours, (b) 3.25 hours, (c) 3.5

hours, (d) 3.75 hours, (e) 4 hours, (f) 4.5 hours, (g) 5 hours, (h) 5.5 hours, and (i) 6 hours

(reproduced from Qi et al. (2016)).

Qi et al. (2016) identified that the primary component of the carbon spheres was HMF molecules.

When the concentration of HMF in the solution was sufficiently high, they polymerised into solid

carbon spheres. Therefore, it can be postulated that the presence of catalysts enhanced the

degradation of sucrose into its respective degradation components, including HMF, which would

then accumulate within the solution faster, promoting the early occurrence of polymerisation.

Regardless, there is a noticeable difference in the average diameter of the carbon spheres obtained

68
from the HTC (180 oC, 6 hours) catalysed by levulinic and formic acid, at 470 to 1116 nm,

respectively. The reason behind this significant size disparity, despite both acids working effectively

in catalysing the HTC was attributed to the fact that levulinic acid can also act as a ‘capping agent’

(Figure 8). Levulinic acid would be present in the reaction medium, as HMF can undergo rehydration

to form either formic acid or levulinic acid. They defined ‘capping agent’ as a compound that also

participates in the polymerisation, reducing the surface density of hydroxyl group. This would reduce

the number of polymerisation sites on the surface, eventually capping the whole spheres to prevent

further polymerisation. As a result, new spheres would form instead, and the cycle would repeat.

Therefore, the average particle diameter in the presence of levulinic acid was lower than that of

formic acid.

Figure 8. Schematic illustration of the role of levulinic acid as a 'capping agent' in the formation of

carbon spheres (Reproduced from Qi et al. (2016)).

69
In the baseline study by Qi et al. (2016), the diameter of carbonaceous spheres increased, albeit

relatively slightly. This is due to the degradation of sucrose into hexoses (i.e. glucose and fructose),

where they would degrade into HMF. The formation of secondary deposits followed a similar

mechanism as well, at a lower rate. These formed formic and levulinic acid also would act as a

catalyst for the carbonisation, hence often referred to as a self-catalysing system. Nevertheless,

introducing these catalysts would promote the earlier stages of carbonisation, hence promoting the

formation of carbon spheres. Qi et al. (2016) also studied the effect of mixing both catalysts (0.1 M

levulinic acid and 0.05 M formic acid). The carbon spheres had an average diameter of 258 nm at 3

hours and 887 nm at 6 hours, the values of which lie between those for the carbon spheres obtained

from the two individual catalysts at the previously mentioned concentration. Such mixing of

catalysts thus can be used to manipulate the diameters of these carbonaceous spheres. The key

takeaway is that the addition of acid catalysts can help enhance the formation of these HMF rich

carbon spheres. Since HMF would also degrade into levulinic acid, the concentration of HMF and its

degradation rate affect the size of formed carbon spheres as well.

In the presence of organic acids such as formic acid and levulinic acid (Qi et al., 2016), secondary

formation was observed in the HTC of sucrose. Organic acids, similar to mineral acids, both

promoted the formation of secondary deposition. Elemental composition behaviour when catalyst

was added remained relatively similar to that without catalyst (i.e. high carbon content, relatively

similar hydrogen content, and decreased oxygen content). The addition of formic and levulinic acid

also increased the size of particle diameter, similar to the mineral acid catalysts case. Direct

comparison of particle size formation in the presence of mineral and organic acid catalysts in a

similar setting (reaction condition, precursor, etc.) would provide insightful information. García-

Bordejé et al. (2017) and Qi et al. (2016) reported the reaction mechanism of catalyst addition in the

WT of cellulose and sucrose, respectively. Both reaction mechanisms have similarities, i.e. they

involve the polymerisation of compounds onto the solid hydrochar. Qi et al. (2016) described these

70
compounds as HMF and levulinic acid. Hence, based on the formation of secondary deposits, one

could determine the dominant reaction pathway (i.e. polymerisation or degradation of HMF).

Salt catalysts

Salt catalysts that were studied in HTC were as previously classified: chloride salts (aluminium

chloride (Cai et al., 2016), iron (II) and iron (III) chloride (Abd Hamid et al., 2015)). The discussion

and comparison were made based on the category in Section 5.2.1.

Chloride salts

In the HTC of glucose with aluminium chloride (AlCl3) as the catalyst, Cai et al. (2016) studied the

effect of two different catalyst concentrations (10 and 50 mol. %) at 130 oC and 20 hours. When the

catalyst amount varied from 10 to 50 mol % at 130 oC and 20 hours, the average particle diameter

decreased from 3.90 to 3.17 microns and increased yield from 9.4 to 17.5 wt. % were observed for

10 and 50 mol. % AlCl3, respectively. This indicates that when the concentration of aluminium

chloride was increased, the particle size of secondary deposits decreased, even though the yield

increased. Regardless, no particle size information was provided for its non-catalytic counterpart, so

the effect of aluminium chloride catalyst addition on average particle diameter could not be

determined. These carbonaceous spheres' reaction mechanism (Figure 9) was described to conform

to the classical nucleation theory of homogeneous nucleation model (the LaMer model). The

reaction started with the isomerisation of glucose into fructose, where the fructose then underwent

polycondensation to form HMF. The HMF and levulinic acid present in the reaction medium would

then cross-link via polymerisation-polycondensation reaction. Levulinic acid could be obtained from

the degradation of HMF (Qi et al., 2016). These cross-linking of furanic structures would then lead

to the formation of polyfuranic clusters. When the polyfuranic clusters’ concentration is high

enough, at a point referred to as ‘critical supersaturation point’, a process known as ‘burst

nucleation’ would take place, forming what is referred to as the nucleus. These nuclei would grow

uniformly and isotropically via continuous reaction on the nuclei surface, forming microspheres.

71
 Figure 9. Schematic illustration of the reaction mechanism of carbon spheres from the HTC of

glucose with aluminium chloride as catalyst, and the role of ions from the catalyst in the reaction

mechanism (reproduced from Cai et al. (2016)).

Abd Hamid et al. (2015) studied the HTC of -cellulose in the presence of chloride salts (or Lewis

acid catalysts), FeCl2, and FeCl3 at 220 oC and 12 hours. In the presence of 33 wt. % solution of FeCl2

and FeCl3, the yield of hydrochar was higher than its non-catalytic counterpart, at 66.5 wt. % without

catalyst, 72.8 wt. % with FeCl2, and 72.5 wt. % with FeCl3. In the presence of both catalysts, the

particle size of carbonaceous deposits decreased from 2-3 microns (Figure 10(a)) down to only 0.3-

0.6 microns (Figure 10(b,c)). While the presence of catalyst enhanced the yield, the secondary

formation observed gave rise to a smaller average particle diameter. This could be due to the rapid

formation of secondary deposits, but with limited particle growth, hence the reduced particle size.

They reported that better catalytic activity was obtained in FeCl2 case when compared to FeCl3 case

(i.e. at 220 oC and 24 hours, the yields were 73.5 to 72.9 wt. % for FeCl2 and FeCl3, respectively). The

72
disparity was attributed to the fact that FeCl2 promoted the formation of C=O group, which is less

stable than FeCl3. The catalytic activity was linked to the catalyst's properties, i.e., a Lewis acid and

its oxidation state, which enables the dehydration of the glycosidic bond of the cellulose via

electrophilic attack.

Figure 10. SEM image of hydrochar from the HTC of -cellulose at 220 oC and 12 hours under (a) no-

catalytic condition, (b) catalysed by FeCl2, and (c) catalysed by FeCl3 (reproduced from Abd Hamid et

al. (2015)).

Teh et al. (2015) studied the HTC of glucose and oil palm shell fiber (OPSF) in the presence of a

eutectic mixture of zinc chloride and sodium chloride as catalysts. They studied the elemental

composition (i.e. C, H, N, S) of glucose and OPSF without catalyst at 220 oC and 2 hours. The carbon

content at 220 oC in the presence of catalyst was higher than the baseline, at 63.75 to 62.76 wt. %,

while the hydrogen content is lower, at 2.55 to 4.66 wt. %. Hence, these findings further supported

73
the use of chloride salts as a catalyst allowing the synthesis of hydrochar with relatively high carbon

content. In the study of chloride salts as the catalyst, an increase in yield was observed when

aluminium chloride was used as the catalyst (Cai et al., 2016). Other than aluminium chloride, iron

(II) chloride and iron (III) chloride were also studied (Abd Hamid et al., 2015). Regardless, no direct

comparison can be made between these two studies. In the study of aluminium chloride, Cai et al.

(2016) did not study the effect of catalyst addition with respect to baseline on formed particle size.

Still, they studied the effect of catalyst concentration, where increased concentration led to

decreased average particle size. On the other hand, in the study of iron (II) and iron (III) chloride

(Abd Hamid et al., 2015), they did not study the effect of catalyst concentration on formed particle

size, but a comparison to baseline showed that catalyst addition caused average particle size to be

reduced. Regardless, the observed behaviour in chloride catalysts was different to the observed

behaviours in acid catalysts such as mineral acid catalysts (hydrochloric acid (García-Bordejé et al.,

2017)) and organic acid catalysts (formic and levulinic acid (Qi et al., 2016)). In contrast, with acid

catalysts addition and concentration increase, an increase in particle diameter of secondary deposits

was observed. This indicates that the formation mechanism in the presence of chloride salts would

be different (as elaborated) from that in the presence of mineral or organic acid catalysts. The

changes to elemental composition due to chloride salts such as mixture of zinc chloride and sodium

chloride (Teh et al., 2015) were also similar to other catalysts reviewed so far.

Others

Ming et al. (2013) reported the effect of sulphate salt (Na2SO4) on the diameter of the formed

particle during HTC of glucose for lithium-ion battery application. They reported that the particle

diameter obtained from the baseline run of 180 oC and 5 hours was approximately 0.157 microns.

When 0.1 M Na2SO4 was added, the average particle diameter increased to 7.260 microns, which

showed a drastic increase in diameter compared to the baseline. The postulation behind the particle

diameter promotion was tied to the effect of Na2SO4 catalyst in accelerating the degradation of

74
glucose into intermediates (i.e. HMF), which then underwent polymerisation (or aromatisation),

leading to secondary formation.

Hence, in the presence of sulphate salt such as sodium sulphate (Ming et al., 2013), the behaviour of

the diameter of secondary deposits particle was similar to that of mineral acid catalysts and organic

acid catalysts, where HMF was once again reported to be a key component in the formation of

deposition.

Therefore, in the presence of the catalyst, the formation of HMF-rich carbon spheres was promoted.

For instance, when formic and levulinic acids were introduced as the catalyst in the HTC of sucrose,

carbon spheres' size increased drastically compared to that without catalysts (Qi et al., 2016). Cai et

al. (2016) and García-Bordejé et al. (2017) also reported similar mechanisms for forming these

carbon spheres, where HMF is the constant in all proposed schematics. Various studies (Abd Hamid

et al., 2015; García-Bordejé et al., 2017; Laohapornchaiphan et al., 2017; Ming et al., 2013; Reiche

et al., 2015; Teh et al., 2015) reported that the presence of catalyst alters the size of the

carbonaceous spheres, as previously explained in subsequent sections. García-Bordejé et al. (2017)

and Hasan et al. (2021) also reported that hydrochar obtained from the catalytic HTC had higher

carbon content when compared to the hydrochar without catalyst. Whilst their primary objective is

to create a carbon-rich yield while being able to manipulate the morphology, the key interest to WT

comes from the fact that the formation of these carbonaceous spheres tends to enhance the

product yield. Since they are also rich in HMF, they can contribute to increased HHV. Some findings

also suggested the catalyst's ability to promote the formation of products with higher carbon

content, which was also found to be beneficial to the fuel properties of the hydrochar. Table 5

summarises the results of the studies on catalytic WT and HTC for carbon materials synthesis.

75
 Table 5. Compilation of results from studies on catalytic WT and HTC for carbon materials synthesis.

Precursor Biomass- Catalyst Catalyst Temperature Time Yield (%) Average Elemental composition Ref
o
to-liquid amount ( C) particle
(wt. %)
mass diameter

ratio (m) C H N S O

- 3:50 - - 220 12 hr 66.5 2 to 3 69.2 4.6 - - - (Abd Hamid et al.,

cellulose 2015)
FeCl2 33 wt. % 72.8 0.3 to 0.6 72.5 4.2 - - -

solution
FeCl3 72.5 72.6 4.4 - - -

Micro- 1:5 - - 195 20 hr 32.3 120 68.3 4.5 - - 27.1 (García-Bordejé et al.,

crystalline 2017)
HCl 2M 14.3 220 67.6 4.4 - - 27.9
cellulose

(MCC) 5M 24.7 220 73.5 5.1 - - 21.4

- 40 hr 41.0 40 67.8 4.3 - - 27.6

2M 19.0 230 69.6 4.7 - - 25.7

76
 5M 26.4 450 75.3 5.6 - - 19.0

Fructose 1:9 - - 200 3 hr - 0.85 - - - - - (Modugno & Titirici,

2021)
H2SO4 - (pH 1.5) - 6.60 - - - - -

Sucrose 1.711:50 - - 180 6 hr - 0.29 - - - - - (Qi et al., 2016)

C5H8O3 0.100 M - 0.47 - - - - -

(Levulinic acid)

HCOOH 0.159 M - 1.12 - - - - -

(Formic acid)

C5H8O3 (Levulinic 0.100 M - 0.89 - - - - -

acid) and HCOOH C5H8O3

(Formic acid) and 0.050

M CH₂O₂

Glucose 1.58:25 AlCl3 10 mol. % 130 20 hr - 3.90 - - - - - (Cai et al., 2016)

solution

77
 20 mol. % - 3.80 - - - - -

solution

50 mol. % - 3.17 - - - - -

solution

1:5 H3PO4 - (pH 6) 220 6 hr - 0.50 69.6 5.4 0.4 - 24.8 (Reiche et al., 2015)

- (pH 3) - 1.00 68.6 5.8 < 0.1 - 25.6

- (pH 1) - 4 to 15 67.7 6.4 < 0.1 - 25.9

8:1 - - 180 5 hr 26.0 0.16 66.0 4.1 - - 29.9 (Ming et al., 2013)

Na2SO4 0.1 M 77.0 7.26 66.2 4.6 - - 29.2

2:1 - - 220 12 hr - - 62.8 4.7 0.1 0.6 - (Teh et al., 2015)

2:1 ZnCl2 + NaCl 2.23g per - - 63.8 2.6 0.4 0.5 -

g
(Eutectic mixture)
precursor

Oil palm 2:1 - - 220 12 hr - - 51.6 8.2 9.8 1.3 - (Teh et al., 2015)

78
shell fiber 2:1 ZnCl2 + NaCl 2.23 g per - - 63.2 3.9 0.5 0.6 -

g
(Eutectic mixture)
precursor

79
Addition of catalysts in other applications

In this section, less studied applications of catalytic WT and HTC are discussed, which can be

classified into the following categories: sugar production (Lenihan et al., 2010), pre-treatment

(Rozenfelde et al., 2021; Susanti et al., 2019), ash content removal (Bach et al., 2015a), and

reaction kinetics (Li et al., 2009; Yat et al., 2008). The individual categories are briefly discussed in

their respective sections.

Sugar production

Lenihan et al. (2010) studied the effect of varying phosphoric acid catalyst concentrations from 2.5

to 10.0 wt. % (2.5, 5.0, 7.5, and 10.0 wt. %) on the hydrolysis of potato peels for sugar production

(i.e. glucose, arabinose) at 135 to 200 oC for up to 90 minutes. The concentrations of ‘inhibitors’

were also reported alongside sugar concentrations. ‘Inhibitors’ are compounds that slow or interfere

with the reaction of subsequent processes to which the obtained sugar will be subjected (i.e.

fermentation). Approximately 62 to 84 % of inhibitors were HMF compounds. Levulinic acid, a

known degradation product of HMF, was also considered an inhibitor. Figure 11 shows the

concentration of inhibitors obtained at 200 oC for up to 90 minutes at varying catalyst

concentrations of 2.5, 5.0, 7.5, and 10.0 wt. %. An initial spike in the concentrations of inhibitors was

observed at different catalyst concentrations in a shorter duration (i.e. less than 10 minutes). The

concentrations of inhibitors peaked at 4.65, 4.90, 6.18, and 6.90 wt. % at 2.5, 5.0, 7.5, and 10.0 wt. %

catalyst, respectively. The highest peak of inhibitors was achieved in the addition of 10.0 wt. %

phosphoric acid catalyst. This was due to the accelerated degradation of sugar obtained from the

hydrolysed potato peels into ‘inhibitors’ such as HMF and levulinic acid. After 10 minutes, a

reduction in inhibitor concentrations was observed for different concentrations of catalysts. At 90

minutes, the concentration of inhibitors left were 2.81, 2.40, 1.57, and 1.60 wt. % at 2.5, 5.0, 7.5,

and 10.0 wt. % catalyst, respectively. At increased catalyst concentration, the total concentration of

80
inhibitors was lower at 90 minutes. In the addition of 10 wt. % catalyst, despite initially having the

highest concentration of inhibitors, the total concentration at 90 minutes was the lowest.

This phenomenon can be supported by two possible postulations: (1) further degradation of

inhibitors into compounds that are not classified as inhibitors, and (2) removal of inhibitors from the

liquid medium via other means (i.e. polymerised itself into solids, hence no longer in the liquid

medium). Qi et al. (2016) reported that HMF would degrade into either levulinic acid or formic acid,

whereas Lenihan et al. (2010) reported just levulinic acid from HMF degradation, where it was also

an inhibitor. Arora et al. (2013) reported that formic acid acted as an inhibitor in the enzymatic

hydrolysis experiment that they had conducted. Hence, formic acid could also be considered an

inhibitor. Therefore, the first postulation would be unlikely, as there was a decrease in the

concentration of inhibitors as time progressed. The second postulation was possible based on

reported observation by Qi et al. (2016) and Cai et al. (2016), where HMF and levulinic acid (to an

extent) participated in a polymerisation reaction to form carbon spheres or secondary deposits. This

would lead to the reduction of these aforementioned compounds in the liquid medium. Therefore,

on top of the primary objective of Lenihan et al. (2010) in the context of sugar production, their

reporting also supported the fact that the addition of catalyst would possibly promote the

polymerisation of these ‘inhibitors’ into carbon spheres.

81
 Figure 11. Concentration of inhibitors up to 90 minutes at 200 oC and varying phosphoric acid
catalyst concentrations of 2.5, 5.0, 7.5, and 10.0 wt. % (reproduced from (Lenihan et al., 2010)).

Pre-treatment

In pre-treatment processes, the purpose is to pre-treat the precursor materials prior to subsequent

processes such as enzymatic hydrolysis (Rozenfelde et al., 2021), activated carbon synthesis (Susanti

et al., 2019), and pyrolysis (Su et al., 2020).

Rozenfelde et al. (2021) utilised sulphate salt, i.e. aluminium sulphate (Al2(SO4)3) as the catalyst for

the hydrothermal pre-treatment of rapeseed straw prior to enzymatic hydrolysis. The hydrothermal

pre-treatment was performed at two different concentrations of Al2(SO4)3 (3 and 5 solution wt. %) at

varying times (i.e. 10 to 40 minutes) at 170 oC, with an autogenous pressure of 7.2 bar that comes

from the vapour pressure of water. The purpose of the pre-treatment was to enhance glucose yield

in subsequent enzymatic hydrolysis. The furfural content was measured from the hydrothermal pre-

treatment of rapeseed straw. At 3 wt. % of Al2(SO4)3, the furfural content increased from 0.62 dry

mass % to 3.03 dry mass % of the rapeseed straw as the pre-treatment time increased from 10 to 40

82
minutes. On the other hand, at 5 wt. % of Al2(SO4)3, the furfural content increased from 1.02 dry

mass % to 4.80 dry mass % at 10 and 40 minutes, respectively. Therefore, an increase in the catalyst

weight increased the decomposition rate of the rapeseed straw, specifically its hemicellulose

content, into furfural.

Susanti et al. (2019) studied the HTC of salacca peel at 200 to 250 oC at 5 hours under fixed pressure

(5 MPa) in the presence of citric acid as a pre-treatment before using the hydrochar as precursor

materials for activated carbon synthesis for supercapacitor application. The purpose of the pre-

treatment was to improve the morphology and capacitance of the hydrochar. They reported that

salacca peels pre-treated this way before the activation enhanced the electrochemical performance

of the activated carbon. This was attributed to the higher surface area of the precursor and

increased oxygenated functional group when citric acid was introduced as a catalyst in the HTC.

Similar objectives were also targeted by Su et al. (2020), who utilised WT of rice husk as a pre-

treatment before subsequent pyrolysis. They found that the presence of acidic molten salt (ZnCl2

hydrated with acetic acid) increased the specific surface area of hydrochar pre-treated at 120 oC

from 283.0 to 331.3 m2 g-1. This increase in specific surface area was reported to provide a positive

result in subsequent pyrolysis (i.e. higher bio-oil quality, higher levoglucosan content, etc.). In

another study conducted by Susanti et al. (2021), they used cerium (III) chloride (CeCl3) in the HTC of

similar biomass (salacca peel) at 225 oC for 5 hours under 5 MPa (by N2). They reported that with

cerium (III) chloride's specific surface area of the salacca peel-derived hydrochar was 1264.39 m2 g-1.

The specific surface area of the hydrochar was only 988.89 m2 g-1 without any catalyst. All of these

findings are similar, i.e. the addition of catalyst is beneficial if the specific surface area of the

hydrochar is of great importance.

Ash content removal

Bach et al. (2015a) studied the WT of spruce and birch by pressuring the system with carbon dioxide

(catalysed by carbonic acid) to reduce the ash content in the hydrochar. An increase in WT

83
temperature reduced the ash content of both spruce and birch biomass (i.e. when the temperature

was raised from 175 to 225 oC, ash content decreased from 0.54 to 0.50 wt. %, for spruce and birch,

respectively). The introduction of carbonic acid via carbon dioxide pressurisation (to approximately

70 bar) further reduced the ash content (i.e. when carbon dioxide was used instead of nitrogen, ash

content was reduced from 0.50 to 0.21 wt. % and 0.65 to 0.25 wt. % for spruce and birch,

respectively). The enhanced removal was attributed to the acidity of carbonic acid, which assisted in

removing ash and inorganic contents from the hydrochar.

Reaction kinetics

Li et al. (2009) studied the kinetics of fructose decomposition by degrading it in a high temperature

liquid water (HTLW) and studied the addition of acetic acid and formic acid on the kinetics of the

formation of HMF, furfural, and levulinic acid. Fructose degraded when subjected to HTLW at 180 to

220 oC under 10 MPa (by N2) for up to 100 minutes. When 10.8 mg mL-1 of acetic acid was

introduced as a catalyst for the system, the fructose reached complete conversion at 220 oC after

approximately 10 minutes, as opposed to only around 90 % without catalyst. Fructose conversion

could reach approximately 90 % for HTLW at 180 oC after around 80 minutes. The conversion,

nonetheless only reached 50 % without catalyst. Increase in HMF yield was also reported, where the

yield peaked at nearly 60 % at less than 5 minutes at 220 oC before degradation. On the other hand,

the yield at 180 oC peaked at around 55 % at 80 minutes before degrading to around 50 % at the 100

minutes mark. The addition of catalyst at both reported temperatures showed that the conversion

of fructose increased and the yield of HMF increased. However, the degradation of HMF was more

prominent, where the degradation started at 180 oC following the peak yield (210 oC for baseline). In

the addition of 10.8 mg mL-1 of formic acid, conversion of fructose across all temperatures reached

100 % (or nearly) at different reaction times (i.e. less than 10 minutes for 220 and 210 oC, 20 minutes

for 200 oC, 30 minutes for 190 oC, and 80 minutes for 180 oC. This indicated that formic acid has

better catalytic activity than acetic acid in the degradation of fructose. Intuitively, enhanced

84
degradation in the fructose degradation should also be applicable to the HMF production and

degradation, which was evidenced in the reported HMF yield. Unlike the baseline and acetic acid

catalyst cases, the highest concentration of HMF was no longer obtained at 220 oC. It was achieved

at 210 oC at approximately 59 % in 5 minutes or so. The HMF yield at every studied temperature

reached peak yield faster than acetic acid, where they then also degraded more rapidly in

comparison to the degradation that occurred at 180 oC as early as beyond 30 minutes (i.e. 56 % at 30

minutes to 30 % at 100 minutes). Li et al. (2009) studied the concentration of formic acid at varying

concentrations (i.e. 0 to 13.7 mg mL-1) at 200 oC for up to 30 minutes to understand the effect of

formic acid. They reported that at 13.8 mg mL-1 concentration of formic acid, the conversion of

fructose reached almost 100 % at just 5 minutes, whereas it is as low as slightly above 20 % at 5

minutes, with increasing fructose conversion when catalyst concentration was increased. Fructose

could be converted entirely in the presence of formic acid in any concentration (2.5 to 13.8 mg mL-1)

after 30 minutes, whereas the baseline only reached slightly above 80 %. Nevertheless, conversion

rate was higher at higher concentration, as less time was required to achieve complete degradation.

Based on the reported HMF yield, surprisingly the highest catalyst concentration (13.8 mg mL-1) did

not have the highest HMF yield peak (peaked at around 48 % at 10 minutes). Instead, the highest

peak was achieved at approximately 15 minutes, with catalyst concentration of 8.0 mg mL-1 (around

55 %). This was postulated to be due to the enhanced degradation of HMF into levulinic acid, which

is a commonly reported form of degraded HMF. Li et al. (2009) described the reaction mechanism of

fructose degradation as consisting of two consecutive reactions, where; (1) fructose degrades into

HMF, and (2) HMF degrades into levulinic acid. Based on the reported result, they concluded that

the addition of both acetic and formic acid promoted the degradation of fructose, where acetic acid

promoted the first reaction in the mechanism scheme (fructose to HMF) and formic acid promoted

both reactions (fructose to HMF, HMF to levulinic acid).

Yat et al. (2008) studied the hydrolysis of basswood and switchgrass with diluted sulphuric acid (0.5

g mL-1) to observe the kinetics of formation and degradation of xylose. They reported that the yield

85
of xylose and other sugars (i.e. glucose, galactose, arabinose) were relatively low when the

hydrolysis temperature was below 135 oC, and that the yield of xylose peaked at 175 oC. Glucose,

xylose, and furfural yields of basswood hydrolysis at 175 oC with sulphuric acid catalyst of 0.5 g mL-1

exhibited trend where yield of xylose peaked at approximately 7 wt. % yield at 45 minutes, followed

by degradation until the yield became lower than 0.5 wt. % at 105 minutes. On the other hand,

glucose yield increased steadily up to 4 wt. % at 105 minutes. Interestingly, furfural yield was

relatively low before 40 minutes, with a yield less than 0.1 wt. % at 40 minutes. Beyond 40 minutes,

the yield increased drastically, peaking at slightly above 3 wt. % yield at 105 minutes. The yield of

furfural peaked when the yield of xylose decreased, supporting the statement that furfural was

obtained from the degradation of xylose. Xylose was likely obtained from the degradation of

hemicellulose, which degrades more readily at a lower temperature, while glucose was from the

degradation of cellulose, which would only degrade at a relatively higher temperature.

86
Lesson Learnt and Outlook

Lignocellulosic biomass with high lignin content would lead to hydrochar with high yield, and to an

extent, high HHV. Although biomass generally behaves similarly, as observed by Demirbaş (2001),

where their lignin composition correlates with their HHV, some biomass may behave differently. For

instance, Reza et al. (2015) reported that wheat straw with only 11.69 wt. % lignin content has a

higher HHV than most of the other reported biomass despite their higher lignin content. Besides

lignin, high cellulose content may be beneficial. This is because cellulose would degrade into sugar

compounds (i.e. glucose and fructose), where fructose would then undergo triple dehydration to

form HMF (Qi et al., 2016; Shrotri et al., 2017). These HMF compounds (and their subsequent

degradation product, levulinic acid), would lead to the formation of carbonaceous spheres or

secondary deposits onto the initial hydrochar (Cai et al., 2016; Qi et al., 2016). Given the high HHV

of HMF, which ranges from 22.05 MJ kg-1 (O'Neill, 2006) to 22.06 MJ kg-1 (Kambo & Dutta, 2015),

the presence of such secondary deposits is anticipated to provide both high yield and HHV.

In WT, the temperature effect is more dominant than the other parameters. The recommended

temperature for WT is 180 to 270 oC. No significant changes were observed when operated below

150 oC (Volpe & Fiori, 2017) since 180 oC is the temperature where hemicellulose starts to degrade

(Pauline & Joseph, 2020). Temperature above 270 oC, on the other hand, would lead to marginal

degradation of lignin (Yuliansyah et al., 2010), which would not be beneficial in maximising HHV.

Under an autogenous condition, elevated temperatures would also lead to an exponentially higher

pressure. For instance, the autogenous pressure at 220 and 260 oC are 1.9 and 4.3 MPa, respectively

(Gan et al., 2019). Elevated pressure would raise cost and safety concerns in scale-up applications

(Drennen, 2019).

The effect of residence time is also quite considerable, especially at longer residence time (i.e. up to

72 hours (Soh et al., 2022)). At prolonged residence time, the formation of microspheres was

87
observed. Regardless, the effect of residence time seems to be secondary relative to that of

temperature, as no microspheres were observed below 220 oC (Sevilla & Fuertes, 2009).

On the effect of biomass-to-liquid ratio, lower biomass-to-liquid ratio provided hydrochar with

higher yield and HHV (Volpe & Fiori, 2017). This was due to a more concentrated liquid medium,

which promoted polymerisation to form secondary deposits. Regardless, an optimisation study

performed by Kang et al. (2019) showed that temperature and time had a more prominent effect on

the HHV of hydrochar than biomass-to-liquid ratio.

The effect of pressure was reported to have similar effect to that of increased WT temperature (Yan

et al., 2019). Hydrochar obtained at pressure of 3.1 MPa and temperature of 180 oC was reported to

have HHV similar to that obtained at temperature of 220-250 oC at autogenous condition (Novianti

et al., 2014; Parshetti et al., 2013; Yan et al., 2019). Nitrogen (N2) and carbon dioxide (CO2) were

both utilised to study the effect of pressure in the WT of biomass (Bach & Skreiberg, 2016; Novianti

et al., 2014; Parshetti et al., 2013). Between these two gases, CO2 was reported to lead to hydrochar

with lower yield and HHV.

For heating method, the utilisation of microwave heating method was found to provide positive

results, as hydrochar obtained from microwave-assisted WT gave higher HHV and yield (Dai et al.,

2017; Kang et al., 2019; Shao et al., 2019). Regardless, the application of microwave heating in WT is

still limited. Hence, future studies can look into how this can be used to improve the fuel properties

of hydrochar.

To sum up and compare the effect of these five different operating parameters, Table 6 presents the

relative rank of these parameters. Note that this ordering was made based on the authors’ opinion

with references from the literature survey.

Table 6. Parameters, preference of parameter values, and their importance based on significance.

88
 Parameters Effect Rank

Temperature High 1

Time Moderate 2

Pressure High 1

Biomass-to-liquid ratio Low 3

Microwave heating Present Not yet clear

In terms of the phase, two different types of catalysts have been applied in WT and HTC: solid

(heterogeneous) and liquid (homogeneous) catalysts. Solid catalysts are generally more preferred in

the actual application as they are more environmentally friendly (Takagaki et al., 2008) and

reusable, as they can be recovered easily from the liquid medium following the process.

Nevertheless, solid catalysts may lose their effectiveness with increasing operation cycles due to the

leaching out of acid sites in the liquid medium. Solid catalysts are also not as effective as liquid

catalysts due to various factors responsible for their overall catalytic effectiveness (Takagaki et al.,

2008). On the other hand, liquid catalysts have been widely studied due to their ease of usage.

Unlike solid catalysts, liquid catalysts can be more effective for their homogeneous nature within the

liquid medium. Still, this homogeneous nature may cause problem in some specific cases. For

example, liquid catalysts are difficult to separate from the liquid medium after the reaction, which

leads to the need for treatment or management of the process liquid. Table 7 lists the advantages

and disadvantages of these two catalysts.

Table 7. Advantages and disadvantages of solid and liquid catalysts.

Types Advantages Disadvantages

89
Solid/heterogeneous  Environmentally friendly  Prone to leaching

catalysts  Easy to separate  Complex; reliance on various factors

 Can be re-used to be effective

 Lower overall catalytic activity

compared to liquid catalyst

Liquid/homogeneous  Relatively higher catalytic  Difficult to separate

catalysts effectiveness compared to

solid catalysts

Chemical composition-wise, catalysts that have been used in WT and HTC can come from three

different categories: acid catalysts (i.e. mineral acids, organic acids), salt catalysts (i.e. chloride salts,

triflate salts), and others (i.e. lactate salt, propionate salt, acetate salt, sulphate salt). Table 8

summarises the essential findings from the conducted literature review. For producing hydrochar as

fuel via WT, organic acids such as ascorbic and citric are preferred, given their proven catalytic

effectiveness in enhancing the yield and HHV of hydrochar (Ameen et al., 2022; Faradilla et al.,

2021). Secondary formations were also observed when these two catalysts were used, indicating

enhanced secondary deposit formation. On the other hand, while formic and levulinic acids were not

yet studied in WT and HTC to produce fuel hydrochar, their addition was reported to promote

secondary formation (Qi et al., 2016). Therefore, it is postulated that formic and levulinic acid may

also positively affect the yield and HHV of the hydrochar. Chloride salts such as caesium chloride,

lithium chloride, tin chloride, and zinc chloride were also reported to behave similarly to the

aforementioned organic acids, making chloride salts a potential candidate as catalysts for WT of

biomass (Abd Hamid et al., 2015; Cai et al., 2016; Hasan et al., 2021; Lynam et al., 2012). While

chloride salts also promoted secondary formation, increased concentration was observed to form

carbon spheres with smaller average diameters. In the context of improving HHV, the effect of the

90
average diameters of carbonaceous spheres deposited onto the initial hydrochar is not yet clearly

understood, which should be looked into in future studies. Chloride salts are a promising candidate,

similar to organic acids. Some catalysts inhibited the WT process instead, as observed by the

increased yield but decreased HHV in the presence of these catalysts. Reported catalysts that

exhibited such effects are sodium triflate (Simsir et al., 2019) and calcium formate (Lynam et al.,

2012). Despite the presence of few studies that apply mixtures of catalysts into WT and HTC, no

conclusive trend on effect was observed on the fuel properties of resultant hydrochars. Hence more

research and studies are required for these catalyst mixtures.

Table 8. Summary of effect on studied catalysts from the literature on the synthesised hydrochar

based on its yield, HHV, and observation of secondary formation.

Types Summary of effects

Yield HHV Secondary formation

observation / diameter

Mineral Nitric acid Decreased Increased Increase with concentration

acid
Sulphuric acid Decreased Increased Increase with concentration

Organic Acetic acid Decreased Increased -

acid
Ascorbic acid Increased Increased Observed

Citric acid Increased Increased Observed

Increase with concentration

Formic acid - - Increase with concentration

Levulinic acid - - Increase with concentration

91
Chloride Aluminium chloride - - Decrease with concentration

salts
Caesium chloride Increased Increased Observed

Calcium chloride - - -

Iron (II) chloride - - Decrease with concentration

Iron (III) chloride - - Decrease with concentration

Lithium chloride Increased Increased Observed

Tin chloride Increased Increased Observed

Zinc chloride Increased Increased Observed

Triflate Aluminium triflate Decreased Increased -

salts
Sodium triflate Increased Decreased -

Others Aluminium sulphate - - -

Calcium acetate Insignificant Insignificant -

Calcium formate Increased Decreased -

Calcium lactate Decreased Increased -

Calcium propionate Insignificant Insignificant -

Magnesium acetate Insignificant Insignificant -

Sodium sulphate - - Increase with concentration

Aluminium chloride + Decreased Decreased -

hydrochloric acid

Lithium chloride + acetic Decreased Increased -

92
 acid

Zinc chloride + acetic acid Increased Decreased -

Zinc chloride + sodium - - -

chloride

In hydrochar synthesis for fuel application via WT, some catalysts studied were observed to provide

a positive effect on the hydrochar’s yield and HHV. Some formation of secondary deposits was also

observed, though not yet explored upon in detail. To have more insights, postulations, findings, and

mechanisms from the other related applications have been explored. In carbon material synthesis

via HTC, these secondary deposits were thoroughly analysed, where they are reported to primarily

consist of HMF. Therefore, these secondary deposits observed during hydrochar synthesis are likely

composed mainly of HMF. HMF has a relatively high HHV compared to the other lignocellulosic

components, so these depositions likely enhance the HHV of the hydrochar on top of its yield. The

addition of catalyst promoted the formation of HMF within the liquid medium, as Lenihan et al.

(2010) reported in the hydrolysis of potato peels for sugar production. Reduction in ‘inhibitors’,

where approximately 62 to 84% of these ‘inhibitors’ are HMF were observed to reduce at prolonged

residence time. This reduction can be postulated to be caused by the polymerisation of these HMF

compounds into secondary deposits.

Conclusion and Recommendation

Lignocellulosic biomass with high lignin content would be preferred as a precursor material for fuel

synthesis via WT, though it may not always be the case. Generally speaking, lignocellulosic biomass

with high lignin content has relatively higher HHV, though some biomass have high HHV despite

their low lignin content. Hence, the suitability of lignocellulosic biomass as a precursor varies on a

93
case-by-case basis. In WT, temperature and pressure are more dominant based on their effects on

the properties of synthesised hydrochar. The effect of time is not as significant as temperature and

pressure, but more significant than the biomass-to-liquid ratio of the process (temperature =

pressure > time > biomass-to-liquid ratio). On the other hand, no conclusive finding can be made on

the effect of microwave heating. In catalytic WT of biomass, various types of catalysts have been

studied, which can be classified into solid (heterogeneous) or liquid (homogeneous) catalysts. Both

types of catalysts have their advantages and disadvantages. Liquid catalysts are very effective given

their homogeneous nature but are difficult to separate from the process liquid medium. On the

other hand, solid catalysts are easy to separate, allowing them to be reused easily, at the expense of

relatively lower efficiency than liquid catalysts. For liquid catalysts, it can be further segregated into

the following categories: acid catalysts, salt catalysts, and others (i.e. lactate salt, propionate salt,

acetate salt, and sulphate salt). Among all of these studied catalysts, organic acid (acid catalyst) and

chloride salts (salt catalysts) are relatively more effective than the other studied catalysts based on

the fuel properties of synthesised hydrochar (yield and HHV). These two types of catalysts also

promoted secondary formation on the synthesised hydrochar. The secondary formation observed

correlated with the enhanced yield and HHV of synthesised hydrochar, though there is insufficient

finding to conclude this observation.

As a future recommendation, microwave heating can be studied more comprehensively to have a

more conclusive understanding of its effect on the WT of lignocellulosic biomass. For liquid catalysts,

more research can be conducted on recovering the liquid catalysts from the liquid medium of the

process. On the other hand, if a solid catalyst can have efficiency that approaches those of liquid

catalysts, its ease of separation will be very attractive. The addition of catalysts for the purpose of

fuel production via WT should be explored in more depth based on the formation of secondary

deposits observed. The addition of organic acids and chloride salts and their correlation with the

formation of secondary deposits should be studied comprehensively. The establishment of reaction

mechanism for the formation of secondary deposits due to catalyst addition is a potential research

94
direction to be explored on the WT for fuel synthesis. Techno-economic analyses (TEA) can be

conducted to have a better overview of the advantage of catalyst addition based on its cost of

operation as well, as it is crucial to ensure that the addition of catalysts is beneficial from an

economic perspective.

Declaration of Competing Interest

The authors do not have any conflict of interest statement on this manuscript.

Acknowledgements

The authors acknowledge the financial support from the Malaysian Ministry of Higher Education

(MOHE) through the Fundamental Research Grant Scheme (FRGS/1/2020/TK0/SWIN/03/1).

Frederick Phang and Megan Soh gratefully acknowledge Full Fee-Waiver Studentship provided by

Swinburne University of Technology Sarawak Campus.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be
considered as potential competing interests:

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