Fuel 285 (2021) 119053

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Catalytic hydrothermal liquefaction of biomass into bio-oils and other value- T

added products – A review
Senthil Nagappana, Rahul R. Bhosaleb, , Dinh Duc Nguyenc,d, Nguyen Thuy Lan Chie,
⁎

Vinoth Kumar Ponnusamyf,g,h,i, , Chang Soon Woongd, Gopalakrishnan Kumarj,

⁎ ⁎

a
Department of Biotechnology, Sri Venkateswara College of Engineering, Sriperumpudur, Chennai, Tamil Nadu, India
b
Department of Chemical Engineering, College of Engineering, Qatar University, 2713 Doha, Qatar
c
Institute of Research and Development, Duy Tan University, Da Nang, Viet Nam
d
Department of Environmental Energy Engineering, Kyonggi University, Suwon, Republic of Korea
e
Innovative Green Product Synthesis and Renewable Environment Development Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho
Chi Minh City, Viet Nam
f
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung City 807, Taiwan
g
Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung City 807, Taiwan
h
Department of Medical Research, Kaohsiung Medical University Hospital, Kaohsiung City 807, Taiwan
i
Department of Chemistry, National Sun Yat-sen University, Kaohsiung City 804, Taiwan
j
School of Civil and Environmental Engineering, Yonsei University, Seoul 03722, Republic of Korea

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Hydrothermal liquefaction (HTL) is an effective method for the conversion of biomass into biofuel involving
Hydrothermal liquefaction moderate temperature and high pressure. However, the yield and quality of bio-oil are not sufficient for com-
Biofuel mercialization under normal HTL conditions. In this regard, the review emphasizes the need to select the ap-
Catalyst propriate catalyst for achieving high bio-oil yields with improved quality. Besides, the factors influencing the
Bio-oil
catalytic HTL, including the types of catalyst used in HTL, the mechanism of catalytic-HTL reaction, the effect of
Biochar

Corresponding authors at: Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung City 807, Taiwan (V.K. Ponnusamy).
⁎

E-mail addresses: rahul.bhosale@qu.edu.qa (R.R. Bhosale), nguyenthuylanchi@tdtu.edu.vn (N.T.L. Chi), kumar@kmu.edu.tw (V.K. Ponnusamy),
gopalakrishnanchml@yonsei.ac.kr (G. Kumar).

https://doi.org/10.1016/j.fuel.2020.119053
Received 22 April 2020; Received in revised form 26 June 2020; Accepted 20 August 2020
Available online 03 September 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
S. Nagappan, et al. Fuel 285 (2021) 119053

the catalyst on other HTL products including biochar, aqueous phase extracts, and gas, are discussed in detail.
This review also summarizes by mentioning the barriers to be overcome in catalytic HTL by focusing on pro-
mising approaches.

1. Introduction
Much of the world's energy demand is fulfilled by fossil fuels that
are not indefinitely available. Sooner or later, the worldwide energy
shortage is imminent [1]. Biomass fuel has a lot of promise but has yet
to be commercialized on a large-scale [2–4]. Hydrothermal liquefaction
(HTL) is one of the potential processes for converting biomass, espe-
cially wet biomass, into fuel [5,6]. Compared to other thermochemical
methods, including pyrolysis and gasification, HTL performs at a lower
temperature and thus needs comparatively less energy supply [5]. After
the world oil crisis of 1970, the first hydrothermal liquefaction reactor
at the Pittsburgh Power Research Institute was installed in the same
year [7]. The study used dry wood flour as a feedstock and sodium
bicarbonate as a catalyst. However, the published literature stated that
there were technical problems with the operation of HTL, including
excessive viscosity and sluggish dissolution of solid [7]. The falling oil
prices discouraged further participation in HTL-related work in sub-
sequent years. But now, with a lot of technological changes and a sharp
increase in oil prices, HTL is once again looking appealing.
HTL is operated at a temperature of 280 to 370 °C and a pressure of
10 to 25 MPa for 5 to120 min in the presence of water [5–10]. Four
main products are derived from HTL, including bio-oil, char, aqueous
phase extract, and gas. Bio-oil is one of the most desirable products.
Generally, the yield of bio-oil generated via HTL varies from 24 to 64%,
and the higher heating value (HHV), the calorific value indicator ranges
from 28 to 38 MJ kg−1 [11,12]. The increase in reactor pressure, the
residence time, and the process temperature have demonstrated that
the production of bio-oil and higher heating value (HHV) has improved
to a degree, albeit at the cost of the process economy [6,13,14]. In
addition, another downside associated with bio-oil produced from HTL
operating under normal conditions is that hetero-atomic contents such
as O, S, and N of the bio-oil cannot meet the requirements for standard
biofuel [15,16].
In this regard, catalysts, by reducing the activation energy of the
reaction, offer several advantages, including an increase in bio-oil yield
and biomass conversion efficiency. It was reported that the bio-oil yield
had been increased by 50 to 60% by using a suitable catalyst [17,18].
Catalyst can boost the flow properties of bio-oil and lower the bio-oil
heteroatom content. Moreover, suitable catalysts can also improve the
HHV of the bio-crude [19]. In particular, the catalyst helps to reduce
the temperature required for achieving the higher bio-oil yield via HTL.
For example, the bio-oil yield (29%) of non-catalytic HTL at a high

Table 1
Positive effects of a catalyst on bio-oil yield during HTL.
Feedstock Catalyst Temperature (°C) Time (min) Effect of catalyst on bio-oil yield (% change) Ref.

Nannochloropsis sp. Pd/C 350 60 20 [73]

Nannochloropsis sp. Pt/C 350 60 10 [73]
Nannochloropsis sp. Ru/C 350 60 13 [73]
Nannochloropsis sp. Ni/SiO2-Al2O3 350 60 10 [73]
Nannochloropsis sp. CoMo/γ- Al2O3 350 60 15 [73]
Nannochloropsis sp. Zeolite 350 60 8 [73]
Nannochloropsis sp. Pt/C with H2 350 60 5 [73]
Dunaliella tertiolecta 5% Na2CO3 360 50 5.8 [94]
Spirulina platensis Na2CO3 350 60 11.7 [52]
Chlorella pyrenoidosa NaOH 240–280 30 10 [95]
Chlorella pyrenoidosa Ce/HZSM-5 300 20 33 [96]
Microcystis viridis Na2CO3 300–340 30–60 33 [93]
Nannochloropsis sp. Nano-Si/SiO2 210 60 5.8 [19]
Nannochloropsis sp. Nano-Si/SiO3 230 60 6.8 [19]
Nannochloropsis sp. Nano-Si/SiO4 250 60 9.8 [19]
Dunaliella tertiolecta Co/CNTs 320 30 9 [30]
Dunaliella tertiolecta Ni/CNTs 320 30 5 [30]
Dunaliella tertiolecta Pt/CNTs 320 30 5 [30]
Water hyacinth 0.5 N K2CO3 280 15 2 [49]
Water hyacinth 0.5 N KOH 280 15 3 [49]
Water hyacinth 1 N K2CO3 280 15 6 [49]
Water hyacinth 1 N KOH 280 15 7 [49]
Dunaliella tertiolecta 5 wt% Na2CO3 300 60 7.7 [92]
Microcystis viridis 5 wt% Na2CO3 340 30 7.5 [93]
Enteromorpha prolifera 5 wt% Na2CO3 300 30 2.6 [97]
Spirulina platensis 5 wt% Na2CO3 350 60 11.7 [52]
Chlorella pyrenoidosa 5 wt% Na2CO3 280 30 5 [95]
Nannochloropsis sp. Na2CO3 210 60 1.7 [19]
Nannochloropsis sp. Na2CO3 230 60 3.8 [19]
Nannochloropsis sp. Na2CO3 250 60 4 [19]
Corn stalk 1.0 wt% of Na2CO3 300 30 13.8 [98]
Wood biomass 0.94 M K2CO3 280 15 25.2 [99]
Dunaliella tertiolecta 5% Na2CO3 360 50 25.8 [94]
Pretreated sorghum bagasse Formic acid 300 60 17 [20]
Pretreated sorghum bagasse K2CO3 300 60 39 [20]
Pretreated sorghum bagasse KOH 300 60 18 [20]
Pretreated sorghum bagasse Formic acid 350 60 31 [20]
Pretreated sorghum bagasse K2CO3 350 60 30 [20]
Pretreated sorghum bagasse KOH 350 60 29 [20]
Barley straw K2CO3 300 30 14 [22]

2
S. Nagappan, et al.
temperature of 340 °C was significantly lower than the yield (39%) of
catalytic HTL achieved at a lower temperature of 300 °C with pre-
treated sorghum bagasse [20]. Therefore, the catalytic liquefaction
method can offer opportunities to produce a higher quality bio-oil with
better yield when compared to the non-catalytic liquefaction.
In addition to the favourable outcomes, the application of catalysts
was responsible for some unfavourable findings also. For instance, by
using acetic acid or sulfuric acid as catalysts, the bio-oil yields were
decreased to ~ 15%, together with an improvement in the solid residue
yield by 1.6–3.2% [21]. Careful consideration of the catalytic HTL
process and the choice of suitable catalysts are essential.
Using a broad literature survey, the difference in yield and physi-
cochemical properties of bio-oil between catalytic and non-catalytic
HTL is discussed. In addition, the reaction process by which the catalyst
attempts to increase the yield of bio-oil- the primary HTL component is
also provided. Specifically, the catalytic types, homogeneous and het-
erogeneous, and their advantages and disadvantages are discussed in
detail. In addition to bio-oil, the study also addresses how the catalyst
impacts other HTL products, including biochar, gas, and aqueous phase
extract. Finally, the knowledge gap required to be resolved in the cat-
alytic HTL is addressed in the ‘Perspective and Challenges’ section.
2. Catalytic effect on bio-oil yield
Various feedstocks have been used for producing bio-oil through
catalytic HTL. One of the crucial factors affecting the yield of bio-oil is
the type of catalyst. The studies in which bio-oil yield was improved
due to the application of catalysts are reported in Table 1. Particularly,
alkali was observed to be a more promising catalyst for HTL. The ad-
dition of K2CO3 in hydrothermal liquefaction of pretreated sorghum
bagasse achieved a 40% increase in bio-oil yield (Table 1). Other alkali
catalysts, including Na2CO3 and KOH, also displayed a more consider-
able increase in bio-oil yield (more than 30% increase). It was under-
stood that some of the acid catalysts, such as sulphuric acid, were re-
sponsible for a reduction in the yield of bio-oil [22]. Table 2 shows the
negative effect of the catalyst on bio-oil yield. But the yield of bio-oil
achieved by using organic acetic acid and formic acid (as a catalyst) was
higher than the alkali based catalyst. Among acids, acetic acid was
observed to be better than formic acid in terms of a higher bio-oil yield
[23]. Even though the use of organic acid catalysts like acetic acid and
formic acid increased the yield of bio-oil, they were found to be con-
sumed during the reaction suggesting that they behave more like a
reactant than a catalyst [23]. According to some studies, the yield of
bio-oil obtained by using a heterogeneous catalyst was also shown to be
promising as compared to the homogenous catalyst [7,24].
The inconsistent data on bio-oil yield reported in the previous
paragraph can be attributed to the difference in the composition of
feedstock [7,21]. The lipid and protein-rich feedstock are better sources
of bio-oil, whereas carbohydrate-rich feedstock is more suitable for
biochar [22,25–27]. For instance, Chlorella, with high lipid content, is
capable of generating more bio-oil than Spirulina which has a low lipid
content (using Na2CO3 catalyst in both cases) [23]. A study involving
HTL of model compounds showed that the utilization of Na2CO3 as a
Table 2
Negative effects of catalyst on the yield of HTL derived bio-oil.
Feedstock Catalyst Temperature (°C)
Pretreated sorghum bagasse Nickel phosphate 300
Pretreated sorghum bagasse Nickel phosphate 350
Nannochloropsis sp. Ru/Cwith H2 350
Nannochloropsis sp. Ni/SiO2-Al2O3 with H2 350
Nannochloropsis sp. Como/γ- Al2O3 with H2 350
Nannochloropsis sp. Zeolite with H2 350
Spirulina platensis Ca3(PO4)2 350
Spirulina platensis NiO 350
3
Fuel 285 (2021) 119053
catalyst had improved the yield of bio-oil from carbohydrates [28].
3. Use of catalysts in HTL
Two catalytic routes are recognized for improving the yield and
properties of the bio-oil: a) use of homogeneous catalysts, including
organic acids or alkali catalysts, and b) use of heterogeneous catalysts,
including transition metal oxide, insoluble inorganic salts, molecular
sieves, altered molecular sieves, supported metals, and others.
3.1. Homogenous catalysts
Broad-spectrum of homogeneous catalysts that have been examined
for the HTL includes 1) alkaline compounds such as K, Na, and Ca forms
of hydroxides and carbonates, 2) organic acids such as formic acid and
acetic acid, and 3) inorganic acids like sulphuric acid. At room tem-
perature, the homogeneous catalysts used for the HTL are soluble in
water.
Homogeneous catalysts are inexpensive and, in some cases, have the
benefit of processing liquid without having to suffer from coking [29].
However, there are also a few drawbacks associated with homogenous
catalysts. When using homogeneous catalysts [30], the separation steps
with high energy consumption and cost are needed for the recovery of
the catalyst. Another downside is the corrosiveness of the homogeneous
catalysts, which is a significant factor that needs to be addressed during
the selection of the material of construction for the HTL reactor [31].
3.1.1. Alkali-based catalysts
Alkali as a catalyst for HTL, has been shown to improve the biomass
conversion primarily by improved depolymerization [20,22]. Through
the process of deoxygenation, desulfurization, and denitrogenation al-
kali can reduce the heteroatom content of bio-oil [8]. Besides, the
carbon and H2 content of the bio-oil can increase due to the application
of alkali catalysts [20,22]. As shown in Table 1, 2, and 3, the yield and
HHV of the bio-oil obtained from alkali catalyzed HTL is always higher
than the non-catalytic HTL. Particularly, it can be seen that alkali is
efficient towards the conversion of carbohydrate-rich biomass. In ad-
dition to the above-mentioned advantages, the use of alkali as catalysts
can decrease the formation of solid residues. Usually, a high amount of
solid residues are generated from lignin-rich biomass such as wood
during non-catalytic HTL, which is not desirable [32,33]. However, the
use of alkali catalyst including Potassium hydroxide and potassium
carbonate successfully liquefies lignin in woody biomass, and thus re-
duce solid formation [31]. Apart from that, Alkali is also known to
promote the hydrolytic depolymerization of other lignocellulosic
polymers, including hemicelluloses and cellulose [32]. Particularly,
according to Torr et al. [7], the alkali catalyst K2CO3 seems to be more
advantageous than the Na2CO3 in the case of HTL of woody biomass.
Studies showed that K2CO3 is better than KOH for the HTL process
[34,35]. K2CO3 and water react together to form bicarbonate and hy-
droxide [22]. The bicarbonate is a secondary catalyst which helps to
improve the bio-oil yield. Moreover, the potassium salt is known to
enhance the re-polymerization of bio-oil products, thus escalating the
Time (min) Effect of catalyst on bio-oil yield (% change) Ref.
60 −5 [20]
60 −1 [20]
60 −1 [73]
60 −5 [73]
60 −3 [73]
60 −5 [73]
60 −5.4 [52]
60 −9.7 [52]
 Table 3
Effect of catalyst on the elemental composition of bio-oil obtained via HTL.
Catalyst Biomass Temperature (°C) Catalytic effects on biocrude (wt%) Non Catalytic effects on biocrude (wt%) % change due to Catalytic effects on biocrude (wt%) Ref.
S. Nagappan, et al.

C H O N S HHV C H O N S HHV C H O N S HHV

Pd/C Nannochlropsis sp. 350 73.4 10.8 9.01 3.9 0.5 38.6 76.4 16.8 11.0 10.8 38.5 38.9 −3.0 6.0 −2 −7 −38 0.3 [73]
Pd/C Nannochlropsis sp. 350 74.9 10.6 9.0 4.2 0.6 38.9 75.9 14.6 11.0 4.2 23.6 38 −1 4.0 −2 0.5 −23 1.0 [73]
Pt/C Nannochlropsis sp. 350 75.9 10.8 8.48 4.04 0.72 39.60 76.9 16.8 16.4 7.04 14.7 36.60 1.0 −6.0 −8 −3 −14 3.0 [73]
Pt/C Nannochlropsis sp. 350 76.1 11.1 8.3 3.9 0.6 40.1 77.1 20.1 18.3 9.9 26.6 36.1 1.0 −9.0 −10 −6 −26 4.0 [73]
Pt/Al2O3 Microalgae 350 74 10.2 12.0 3.6 0.1 38.2 83.0 26.2 49% 15.6 0.1 27.1 9.0 −16 −37 −12 0 11.0 [42]
Pt/Al2O3 Chlorella vulgaris 350 74.8 9.7 9.3 5.6 0.6 37.9 80.8 22.7 46.3 10.6 0.6 29.9 6.0 −13 −37 −5 0 8.0 [42]
Ni/SiO2-Al2O3 Nannochlropsis sp. 350 75 10.2 8.59 3.74 0 38.3 75 10.2 14.5 14.7 0 39.3 0 0 −6 −11 0 −1 [73]
Ni/SiO2-Al2O3 Nannochlropsis sp. 350 76.2 10.7 9.01 3.64 0 39.4 77.2 10.6 11.0 16.6 0 41.4 1.0 5.0 −2 −13 0 −2 [73]
Ni/Al2O3 NO. 350 77% 9.40 10.2 3.6 0 38.2 90.0 12.4 56.2 15.6 0 27.2 13.0 7.0 −46 −12 0 11.0 [42]
Ni/Al2O3 Microalgae 350 75.4 9.70 12.6 5.40 0 34.5 82.4 31.7 27.6 13.4 0 36.5 7.0 −22 −15 −8 0 −2 [42]
Ni–Mo/Al2O3 Chlorella vulgaris 340 73.4 10.3 11.3 4.88 0 37.53 72.5 9.79 12.4 5.2 0 36.3 0.8 0.5 −1.0 −0.3 0 1.23 [100]
Como/γ- Al2O3 Nannochlropsis sp. 350 75.7 10.3 8.50 4.31 0.58 38.8 76.7 10.2 15.5 1.31 31.5 36.8 1.0 1.0 −7 3.0 −31 1.0 [73]
Como/γ- Al2O3 Nannochlropsis sp. 350 74.8 10.4 8.55 3.99 0.56 38.6 75.8 10.3 15.5 8.9 33.5 38.6 −1 2.0 −7 −5 −33 0 [73]
Co/Mo/Al2O3 Microalgae 350 77 8.9 9.4 5 0 37.6 64 7.9 60.4 3.0 0 28.6 13.0 1.0 −51 2.0 0 9.0 [42]
Co/Mo/Al2O3 Chlorella vulgaris 350 75.2 8.3 10.7 5.7 0% 36.2 69.2 11.3 38.7 8.7 0 33.2 6.0 −3 −28 −3 0 3.0 [42]
Zeolite Nannochlropsis sp. 350 69.6 9.44 9.46 4.33 0.74 35.4 77.6 16.4 6.46 8.33 12.7 43.4 −8 −7 3.0 4.0 −12 −8 [73]
Zeolite Nannochlropsis sp. 350 74.2 10.5 8.92 4.05 0.88 38.5 75.2 7.50 11.9 7.05 5.88 38.50 −1 3.0 −3 −3 5 0 [73]
HZSM-5 Dunaliella tertiolecta 360 72.4 8.28 14.7 4.46 0 33.67 75.4 15.2 41.7 5.46 0 39.67 −3 −7 27 1.0 0 −6 [101]
Ru/C Nannochlropsis sp. 350 72.6 10.3 9.34 3.49 0.31 37.5 76.6 9.3 7.34 20.4 63.3 40.5 −4 1.0 2.0 −17 −63 −3 [73]
Ru/C Nannochlropsis sp. 350 73.2 10.6 8.63 3.33 0.42 38.40 76.2 6.60 14.6 23.3 50.4 38.4 −3 4.0 −6 −20 −50 0 [73]
Nano-Ni/SiO2 Microalgae 210 73.1 10.8 12.8 2.97 0.32 37.93 71.8 10.0 13.8 3.77 0.42 36.16 1.33 0.8 −0.9 −0.8 −0.1 1.77 [19]
Na2CO3 Microalgae 210 73.3 10.9 12.0 3.76 0.33 38.31 71.8 10.0 13.8 3.77 0.42 36.16 1.51 0.9 −1.7 −0.0 −0.1 2.15 [19]
Zeolite Microalgae 210 73.3 11.0 12.6 2.99 0.31 38.3 71.8 10.0 13.8 3.77 0.42 36.16 1.56 1 −1.2 −0.7 −0.1 2.14 [19]

4
Co/Mo Chlorella 210 75.2 8.3 10.7 5.7 0 36.2 70.7 8.6 14.8 5.9 0 35.1 4.5 −0.3 −4.1 −0.2 0 1.1 [42]
Ni/Al Chlorella 210 75.4 6.7 12.6 5.4 0 34.5 70.7 8.6 14.8 5.9 0 35.1 4.7 −1.9 −2.2 −0.5 0 −0.6 [42]
Pt/Al Chlorella 210 74.8 9.7 9.3 5.6 0.6 37.9 70.7 8.6 14.8 5.9 0 35.1 4.1 1.1 −5.5 −0.3 0.6 2.8 [42]
Co/Mo Nannochloropsis 210 77 8.9 9.4 4.6 0 37.6 68.1 8.8 19 4.1 0 34.5 8.9 0.1 −9.6 0.5 0 3.1 [42]
Ni/Al Nannochloropsis 210 76.8 9.4 10.2 3.6 0 38.2 68.1 8.8 19 4.1 0 34.5 8.7 0.6 −8.8 −0.5 0 3.7 [42]
Pt/Al Nannochloropsis 210 74 10.2 12 3.6 0.1 38.2 68.1 8.8 19 4.1 0 34.5 5.9 1.4 −7 −0.5 0.1 3.7 [42]
Co/Mo Soya oil 210 77.6 10.4 11.5 0.6 0 39.7 76 10.8 12.5 0.7 0 35.7 1.6 −0.4 −1 −0.1 0 4 [42]
Ni/Al Soya oil 210 82.5 12 5.1 0.3 0 42 76 10.8 12.5 0.7 0 35.7 6.5 1.2 −7.4 −0.4 0 6.3 [42]
Pt/Al Soya oil 210 73.3 10.5 15.6 0.6 0 38.2 76 10.8 12.5 0.7 0 35.7 −2.7 −0.3 3.1 −0.1 0 2.5 [42]
Pt/Al Chlorella pyrenoidosa 240 61.8 8.2 20.5 9.5 0 – 71.3 8.7 10.9 9.1 0 – −9.5 −0.5 9.6 0.4 0 0 [45]
Pt/Al Chlorella pyrenoidosa 300 71.3 8.7 10.9 9.1 0 – 71.3 8.7 10.9 9.1 0 – 0 0 0 0 0 0 [45]
Pt/Al Chlorella pyrenoidosa 300 71.5 9.1 10.7 8.7 0 – 71.3 8.7 10.9 9.1 0 – 0.2 0.4 −0.2 −0.4 0 0 [45]
Raney-Ni Chlorella pyrenoidosa 300 70.8 8.6 11.3 9.3 0 – 71.3 8.7 10.9 9.1 0 – −0.5 −0.1 0.4 0.2 0 0 [45]
HZSM-5 Chlorella pyrenoidosa 300 70 8.7 12.4 8.9 0 – 71.3 8.7 10.9 9.1 0 – −1.3 0 1.5 −0.2 0 0 [45]
HT Woody biomass 300 63.6 5.8 30.5 0.09 0 24.3 71.3 6.2 22.4 0.09 0 29 −7.7 −0.4 8.1 0 0 −4.7 [31]
Colema-nite Woody biomass 300 67.9 5.8 26.3 0.05 0 26.6 71.3 6.2 22.4 0.09 0 29 −3.4 −0.4 3.9 −0 0 −2.4 [31]
K2CO3 Woody biomass 300 65.6 6.2 28.1 0.06 0 26 71.3 6.2 22.4 0.09 0 29 −5.7 0 5.7 −0 0 −3 [31]
KOH Woody biomass 300 66.5 6.1 27.3 0.09 0 26.3 71.3 6.2 22.4 0.09 0 29 −4.8 −0.1 4.9 0.03 0 −2.7 [31]
Feso4 Woody biomass 300 67.5 8.9 23.5 0.12 0 31.3 71.3 6.2 22.4 0.09 0 29 −3.8 2.7 1.1 0.03 0 2.3 [31]
HT/KOH Woody biomass 300 65.4 8.6 25.9 0.11 0 29.8 71.3 6.2 22.4 0.09 0 29 −5.9 2.4 3.5 0.02 0 0.8 [31]
Mgo Woody biomass 300 66.4 6.6 26.9 0.12 27.1 71.3 6.2 22.4 0.09 0 29 −4.9 0.4 4.5 0.03 0 −1.9 [31]
K2CO3 Barley straw 300 67.8 7.62 23.1 0.75 0.56 27.29 62.6 6.42 29.7 0.69 0.51 24.87 5.26 1.2 −6.5 0.06 0.05 2.42 [22]
Na2CO3 Nannochloropsis 300 51.8 7.2 19.1 4.8 0.1 23.56 66.6 9.23 13.1 4.59 0.24 31.92 −14.8 −2.0 5.9 0.2 −0.1 −8.36 [23]
Na2CO3 Nannochloropsis 300 35.8 4.8 14.8 2.5 0.14 17.66 55.6 7.83 12.0 3.76 0.39 25.89 −19.7 −3.0 2.8 −1.2 −0.2 −8.23 [23]
Na2CO3 Nannochloropsis 300 35.2 4.72 15.0 1.68 0 16.96 50.2 6.96 1.88 2.22 0.28 21.41 −14.9 −2.2 13 −0.5 −0.2 −4.45 [23]
Na2CO3 Pavlova 250 60.6 10.5 6.95 3.06 0.36 27.03 54.9 6.04 2.41 4.83 0.2 24.57 5.67 4.5 4.5 −1.7 0.16 2.46 [23]
Na2CO3 Pavlova 300 53.2 8.4 7.54 2.49 0.18 26.49 43.0 4.41 8.54 3.19 0.65 21.75 10.19 3.9 −1 −0.7 −0.4 4.74 [23]
Na2CO3 Pavlova 350 52.7 10.0 2.54 2.3 0.26 20.54 37.3 3.58 12.7 2.58 0.67 15.06 15.43 6.4 −10 −0.2 −0.4 5.48 [23]
Na2CO3 Isochrysis 250 38 4.94 37.1 4.67 0.32 15.82 62.8 9.49 34.8 3.29 0.35 31.68 −24.8 −4.5 2.3 1.3 −0.03 −15.8 [23]
(continued on next page)
Fuel 285 (2021) 119053
S. Nagappan, et al. Fuel 285 (2021) 119053

non-polarity of bio-oil. The rise in the non-polarity facilitates better

[23]
[23]
[21]
[21]
Ref.
separation of bio-oil from water. Besides, the K2CO3 is better than KOH
for the scale-up of HTL since, unlike hydroxide, the K2CO3 does not
cause corrosion [15]. Alkali catalysts, majorly the hydroxides, are
−15.09
−19.3
known to cause corrosion in the HTL reactor [36].
−1.7
HHV

−10
% change due to Catalytic effects on biocrude (wt%)

3.1.2. Acid-catalysts
−0.29
−0.64

Organic acids as catalysts improve the flow properties of bio-oil by

decreasing the viscosity and fraction of high boiling compounds.
0
0
S

However, the application of these catalysts increases the yield of gas-

−0.3
−0.8
−0.4
−0.4

eous compounds as the organic acids are converted into gases during
HTL [37]. Additionally, acids like sulphuric acid enhance the de-
N

gradation of biomass [38]. In comparison to alkali catalysts, the organic

acid-based catalysts are not efficient in reducing the heteroatom con-
2.6
10.
30
38
O

tent of bio-oil [8]. For example, the sulphur content was found to be
doubled when the organic acids were used as the catalysts in place of
−5.8
−4.3
−0.4
−4.1

alkali catalysts (Table 3).

H

3.2. Heterogeneous catalysts

−32.7
−22.1
−1.7
−6.5
C

Heterogeneous catalysis is mostly known for its use in gasification

processes. However, presently several heterogeneous catalysts have
30.95
21.77
HHV

29.5
29.5

also been extensively studied for HTL. This includes metals such as Pt,
Pd, Mo, Ni, Ru, and others supported on active carbon, SiO2, Al2O3, and
Non Catalytic effects on biocrude (wt%)

zeolite [39]. In addition, the molecular sieve catalysts and metal oxide
0.29
0.64

catalysts were also utilized. Heterogeneous catalysts are presumed to

S

have a lower bio-oil yield in comparison to the homogenous catalysts.

2.74
2.12
3.9
3.9

Contrastingly, some studies have shown promising results for the het-
N

erogeneous catalysts in HTL processes. In a study involving the use of

7.44
0.04
20.1
20.1

both homogenous (KOH and formic acid) and heterogeneous catalysts

O

(FeS) for the HTL of waste newspaper and paper mill sludge/secondary
8.49
5.88

pulp, the FeS had shown to have the highest bio-oil yield of around 30%
6.8
6.8

[40]. Similarly, the iron ore catalyst was shown to be more effective
H

than other homogenous catalysts for bio-oil production [41].

58.7
41.5
69.2
69.2

Chen et al. [30] reported that the application of heterogeneous

C

catalysts shown to increase the HHV (by 10%), and quality of bio-oil by
11.56

promoting deoxygenation. According to Xu et al. [8] the Pt/C catalyst

HHV

6.68
27.8
19.5

produced bio-crude with the highest C and H content and HHV. The
same research study also points out that the CoMo/γ-Al2O3, Ni/SiO2-
Catalytic effects on biocrude (wt%)

Al2O3, and Pt/C catalysts promote better deoxygenation while Ru/C

0
0
0
0
S

catalyst shows higher desulphurization and denitrogenation activity.

2.43
1.32
3.5
3.5

Heterogeneous catalysts are also capable of removing a part of O2 from

N

the biomass via gasification [7].

37.5
38.6
22.7

In comparison to the homogenous catalysts, heterogeneous catalysts

31
O

showed better selectivity towards the HTL reactions [31]. Ni/Al2O3

2.69
1.55

catalyst is more selective towards lipids for deoxygenation while Co/

6.4
2.7
H

Mo/Al2O3 and Pt/Al2O3 promote deoxygenation of carbohydrates [42].

Ni-Mo/Al2O3, rather than Ni alone, had superior production and quality
25.9
19.3
67.5
62.7
C

of bio-oil, suggesting that the bimetallic catalyst is a better option [43];

Temperature (°C)

Zirconia is capable of improving the conversion of fatty acids mainly

into acetic acid, alkene, and 2-Nonadecanone [44]. On the surface of
zirconia, amphoteric sites are found in high density because of which it
can theoretically facilitate base as well as acid-catalyzed reactions.
300
350
300
300

Heterogeneous catalyst, Raney-Ni, is known for hydrogenation activity,

particularly at low temperatures [45].
Enteromorpha prolifera
Enteromorpha prolifera

The advantages of heterogeneous catalysts include better recovery

and no corrosion [22]. Heterogeneous catalysts are also known to
promote the stability of bio-oil. For instance, the H form of Zeolite
Isochrysis
Isochrysis

Socony Mobil-5 (HZSM-5) increases the bio-oil stability by reducing the

Biomass

organic acid content and by increasing the fraction of alkene, alkane,

Table 3 (continued)

and ketones [46].

Sulfuric acid

3.3. Catalysts recovery

Acetic acid
Catalyst

Na2CO3
Na2CO3

Reuse of catalysts is very much essential for the economical pro-

duction of HTL bio-oil, especially in the case of metal catalysts, which

5
S. Nagappan, et al.
are costly. The catalyst recovery is a tedious process during which the
quantity as well as the quality of the catalyst gets affected. According to
a study, catalyst reuse can be done not more than 3 times [19]. One of
the current studies shows that the recovery of the heterogeneous cat-
alyst containing Ni was 62% and 18% after 1st and 2nd recycles, re-
spectively. Besides, in the third recycle, a complete loss of catalyst was
noticed [19]. In another example, the surface area of Pt/γ-Al2O3 was
decreased more than 60% after three recycles (due to the coke de-
position) [43].
The reuse of catalyst requires the catalyst to be active. Catalytic
deactivation happens due to the blocking of catalyst pores or coking
[47]. For instance, the use of Pd/C catalyst has shown deterioration
during the third run of HTL, whereas no such limitations were observed
for Pt/C catalyst [8]. In order to overcome the deactivation of the
catalyst, a research group performed catalytic hydrothermal liquefac-
tion in a two-chamber reactor that mechanically separated a carbon-
supported platinum catalyst from biomass and other solid content via a
porous metal frit [48]. Otherwise, a two-step process involving optimal
catalytic conditions for achieving maximum bio-oil yield followed by
catalytic up-gradation can also prevent catalyst deactivation. To sum
up, the usage of robust catalysts and innovative, efficient strategies to
avoid catalytic deactivation and enhance catalytic recovery may be
helpful in improving the process economy of HTL.
4. Mechanism
Lignocellulosic biomass contains carbohydrate polymers, including
cellulose, hemicellulose, and lignin. The polymers are held tightly by
glycosidic bonds. The glycosidic bonds are broken, resulting in the
formation of an organic acid; a reaction is mainly known to be ac-
celerated by alkali-catalysts [22,49,50]. The organic acids formed fur-
ther enhance the degradation of lignocellulosic polymers. Lignin, a
highly recalcitrant polymer in normal conditions, is shown to be
cleaved nicely in the presence of alkali in hydrothermal conditions
[51]. Alkaline hydrolysis of lignin and subsequent hydrolysis of
methoxy group produces phenol derivatives such as 1,2-benzenediol,
3,4-dimethoxy-phenol, and 2-methoxy-phenol [7,52]. Bio-oil produc-
tion via alkali catalyzed hydrothermal decomposition of lignin-rich
birchwood sawdust was shown to increase tremendously from 18 to
40% [31]. This signifies the great assistance of alkali catalysts in the
hydrolysis of lignocellulosic biomass, particularly lignin-rich biomass.
Unlike glycosidic bonds of carbohydrate, the peptide bonds in
protein are relatively stable under hydrothermal conditions [7]. In this
aspect, a study had shown that hydrolysis of protein could be enhanced
by the use of acid catalysts. In that study, the yield of the amino acid
(product of protein hydrolysis) was found to be increased from 4 to 15%
under acidic conditions induced by CO2 during the HTL of Bovine
Serum albumin [53].
After initial hydrolysis, series of intermediate reactions including
isomerization, cracking, substitution, oxidation, dimerization of amino
acids, decarboxylation, deoxygenation, dehydration, denitrogenation
and hydrogenation, are also initiated [5,7,9,54]. As a consequence,
compounds that are mainly reactive free radicals are generated.
If hydrogen content is not sufficient enough to cap the free radicals,
then free radical compounds start to associate itself to form char. One
such reactive species is 5-HMF, which is also the main component of the
bio-oil produced via acid catalyst in lignocellulosic HTL. The 5-HMF
tends to form hydrothermal char/solid via polymerization [28]. Titirici
et al. [55] compared the solid hydrothermal carbon materials asso-
ciated with starch, sucrose, maltose, and glucose by using 13C solid-
state CP-MAS NMR and reported 5-HMF as the core structure of all the
hydrothermal carbon materials. With the help of advanced solid-state
13C NMR techniques, Baccile et al. [56] characterized hydrothermal
carbon allied with glucose and found that 65% of it existed in the form
of HMF ring structure. Based on these studies, it was understood that
the formation of residual solids from 5-HMF caused the decrease in the
6
Fuel 285 (2021) 119053
yields of bio-oil under acidic conditions [28].
Maillard reaction, which occurs between reducing sugar and amino
acids, promotes the formation of solids during HTL [57]. The amount of
pyrazine, a compound produced via Maillard reaction, was found to be
low when acid catalysts were used [58]. This indicates that the addition
of acid catalyst suppresses the Maillard reaction, in turn, solid residue/
char formation.
5. Physicochemical properties of catalytic bio-oil
In general, bio-crude produced from HTL is a viscous dark brown
fluid that includes several organic compounds such as phenol, ketones,
alcohols, esters, aldehydes, acids, and guaiacols [59,60]. These organic
compounds determine the physicochemical properties of bio-oil, in-
cluding HHV value, flow properties, pH, elemental composition, and
thermal stability. In order to improve the physicochemical properties of
bio-oil catalysts can be used. Table 3 shows the % change in C, H, O, N,
and S as well as HHV of bio-oil due to the addition of catalyst in HTL.
HHV is the amount of heat generated from the combustion of a
specific quantity of biomass. Fuel with higher HHV value is desirable.
HHV is given by the formula [61],
HHV = −1.3675 + 0.3137 × C + 0.7009 × H + 0.0318 × O (1)
Obviously, HHV value depends on high hydrogen, followed by
carbon content. Otherwise, we can say that a high H/C ratio is required
for bio-oils application as a fuel. In order to achieve a high H/C ratio,
the rate of decarboxylation and dehydration reaction has to be im-
proved. The decarboxylation or dehydration of aldehydes, acids, alco-
hols, and ketones, which are intermediate products of HTL, lead to the
formation of Hydrocarbons [42,62]. In particular, the conversion of
fatty acid to alkane is seen as one of the important decarboxylation
reactions occurring during HTL. In that case, Alkali catalyst like KOH,
NaOH, Na2CO3, and heterogeneous catalyst like Ni/Al2O3, Pd/C, Pt/C,
Pt/Al2O3, metal oxide catalysts like ZrO2, CeO2, Y2O3, Raney-Ni, HZSM-
5, were seen to promote decarboxylation of fatty acids to alkanes [7,8].
Thus, these catalysts by increasing the proportion of hydrocarbon in
bio-oil improve the H/C ratio significantly, in turn increasing the HHV
value.
Thermal stability, and reduction in the viscosity of bio-oil can be
achieved through deoxygenation reaction [18]. Deoxygenation occurs
mainly through dehydration, decarboxylation, and hydrogenation
[29,63]. For example, phenol undergoes hydrogenation and dehydra-
tion to form to cyclohexane during HTL [64]. Phosphoric acid, Metal
oxide-based catalyst including Ni/ZrO2, Ni/Al2O3, carbon-supported
metals such as Rh/C, Ru/C, Pt/C, and sulphide forms of nickel-mo-
lybdenum, cobalt-molybdenum, and nickel-tungsten catalysts are
known to deoxygenate phenol [64–66].
As said earlier, hydrogenation facilitates oxygen removal from
biomass. Also, Hydrogenation caps the reactive species, which others
contribute to the thermal instability of bio-oil. In this respect, the use of
catalysts, including Ni Ru, Pd, Pt, Co, and formic acid, were shown to
promote hydrogenation [8,18,67]. Moreover, hydrogenation can help
in decreasing the number of heteroatoms in bio-oil, which is possible
through the following mechanism. The hydrogenation of O2 and N2-
containing heterocyclic compound lead to ring saturation, and further,
the cleavage of C-N and C-O bond occurs [68–70].
Removal of heteroatoms like nitrogen and sulphur through deni-
trogenation and desulphurization reaction improves the bio-oil quality.
The presence of nitrogen and sulphur contributes to undesirable NOx
and SOx emission and may also poison catalysts during HTL.
During denitrogenation, nitrogenous compounds are converted to
alkanes through a series of reactions. First, saturation of nitrogenous
compounds occurs followed by C-N bond cleavage, hydrolysis, dehy-
dration, and hydrogenation, eventually resulting in the formation of
alkanes [71]. CoMo/γ-Al2O3, Ru/C, Pd/C, and Rh/C, nitride NiMo/γ-
S. Nagappan, et al. Fuel 285 (2021) 119053

Al2O3, and sulfided NiMo/γ-Al2O3 have shown the capability to convert
pyridine into alkanes like pentane and butane [72]. Desulphurization
happens through hydrogenation followed by desulphurization through
cleavage of C-S bond. The metal catalyst supported on the metal oxide
or carbon support was observed to be suitable for desulphurization
[73].
6. Effect of catalyst on aqueous phase extract of HTL
The mass balance indicates that the significant output of HTL is
aqueous phase extract (APE) (Table 4). The main contributor to the APE
is the decomposition of polysaccharide, including hemicellulose, cel-
lulose, and others [74]. In the case of the alkali catalyst, the APE has a
high pH (8 to 9.5), whereas non-catalytic APE shows pH in the range of
7–8 [23]. The high pH neutralizes organic acid, which accelerates
polymerization required for undesirable char formation [22].
Alkali catalysts increases the total organic carbon (TOC) content of
APE compared to non-catalytic conditions [31,75]. Among the alkali
catalyst, the TOC of APE was higher for carbonates than hydroxide
forms [31,75]. On observation, TOC of APE was found to be mainly
contributed by glucopyranoses and benzenediols [75]. Benzenediols
included 1,6-anhydro-β-d-glucopyranose and benzenediol and 4-ethyl-
1,2-benzenediol [76]. Alkali catalyst increases the fraction of deox-
ygenated sugar products in APE. This is confirmed by the presence of
1,3-cyclopentanediene, alkenes, and cyclic alkanes in APE from alkali
catalyzed HTL [77].
Alkali, such as Na2CO3, was found to increase the nitrogen content
of APE, particularly during HTL of protein-rich biomass, including some
microalgae [23]. This is presumed to be due to the promotion of protein
hydrolysis by alkali [23]. Alkali, such as K2CO3, when used as a catalyst,
increased the metal content in APE during HTL [78]. For instance, Cr
was found in a greater extent in APE of alkali catalyzed HTL of sorghum
bagasse [20]. Again, the presence of chromium in the reactor can be
beneficial since it is known to prevent corrosion [20].
Acid catalysts are known to promote dehydration and condensation
reactions. For instance, the sulphuric acid increased the content of
pyridine and ether in APE compared to the non-catalytic run [79].
Pyridines are obtained from ketones and aldehydes through con-
densation. The degradation of amino acids and carbohydrates produces
ketones and aldehydes [80]. Acid catalysts are also known to promote
the dehydration reaction. Dehydration of glucose in the biomass gen-
erates 5-hydroxymethyl furfural, which subsequently converted to
acetic acid through oxidation [81]. In some cases, glucose dehydration
produces levulinic acid [82]. In addition, small molecular weight car-
boxylic acids, glycerol, and amides were also found in APE from acid-
catalyzed HTL. Acetic acid was found in higher concentrations whereas
glycerol and ether were absent in APE derived from acetic acid cata-
lyzed HTL [21].
In general, catalytic HTL compared to non-catalytic HTL, generates
more macronutrients and micronutrients, including metal in APE. This
provides a valuable opportunity for resource recovery or additional
production of value-added products by utilizing APE for the growth of
commercial strains.
7. Effect of catalyst on the gas fraction of HTL
The gaseous fraction is one of the significant outputs of HTL, which
usually increased in the presence of specific catalysts (Table 4). The
utilization of formic acid, acetic acid, Na2CO3, and KOH was re-
sponsible for the production of 30%, 16–22%, 18–20%, and 10% gases,
respectively [23]. In contrast, some of the catalysts, such as zeolite,
supported the decrease in the yield of gas during HTL [73]. In some

Table 4
Effect of catalyst on yield of bio-oil, gas, solid and aqueous phase extract during HTL.
Feedstock Catalyst Temperature (°C) Time Catalyst Without catalyst Ref.
(min)
Bio-oil Gas (wt Residue (wt Others (wt Bio-oil Gas (wt Residue (wt Others (wt
(wt%) %) %) %) (wt%) %) %) %)

Spirulina platensis Na2CO3 350 60 51.6 12.8 6.5 30.1 39.9 18.3 5.8 36.1 [52]
Spirulina platensis Ca3(PO4)2 350 60 34.5 25 6.4 34.1 39.9 18.3 5.8 36.1 [52]
Spirulina platensis NiO 350 60 30.2 30.5 5.7 33.6 39.9 18.3 5.8 36.1 [52]
Water hyacinth 0.5 N K2CO3 280 15 18 8 19 55 16 11 16 57 [49]
Water hyacinth 0.5 N KOH 280 15 19 6 19 56 16 11 16 57 [49]
Water hyacinth 1 N K2CO3 280 15 22 7 11 60 16 11 16 57 [49]
Water hyacinth 1 N KOH 280 15 23 7 11 59 16 11 16 57 [49]
Wood biomass 0.94 M K2CO3 280 15 33.7 11 4 51.3 8.5 45 39 7.5 [99]
Pretreated sorghum Formic acid 300 60 39 _ 60 _ 22 _ 32 _ [20]
bagasse
Pretreated sorghum K2CO3 300 60 61 _ 20 _ 22 _ 32 _ [20]
bagasse
Pretreated sorghum KOH 300 60 40 _ 22 _ 22 _ 32 _ [20]
bagasse
Pretreated sorghum Nickel 300 60 17 _ 28 _ 22 _ 32 _ [20]
bagasse phosphate
Pretreated sorghum Formic acid 350 60 42 _ 32 _ 11 _ 36 _ [20]
bagasse
Pretreated sorghum K2CO3 350 60 41 _ 23 _ 11 _ 36 _ [20]
bagasse
Pretreated sorghum KOH 350 60 40 _ 50 _ 11 _ 36 _ [20]
bagasse
Pretreated sorghum Nickel 350 60 10 _ 40 _ 11 _ 36 _ [20]
bagasse phosphate
Woody biomass HT 300 30 34.4 0.2 10. 6 54.8 18. 9 0.2 33.4 47.5 [31]
Woody biomass Colemanite 300 30 36.3 0.2 12.1 51.5 18. 10 0.2 33.4 47.5 [31]
Woody biomass K2CO3 300 30 38.5 0.4 14.1 47.1 18. 11 0.2 33.4 47.5 [31]
Woody biomass KOH 300 30 39.5 0.3 12 48.2 18. 12 0.2 33.4 47.5 [31]
Woody biomass FeSO4 300 30 32 0.1 21.9 46 18. 13 0.2 33.4 47.5 [31]
Woody biomass HT/KOH 300 30 35.9 0.3 10.3 53.6 18. 14 0.2 33.4 47.5 [31]
Woody biomass MgO 300 30 30.3 0.4 14.2 55.1 18. 15 0.2 33.4 47.5 [31]
Barley straw K2CO3 300 32 8 56 18 28 52 [22]

7
S. Nagappan, et al. Fuel 285 (2021) 119053

cases, it was also reported that the presence or absence of a catalyst did

[18]
[18]
[18]
[18]
[18]
[17]
[23]
[23]
[23]
[23]
[23]
[23]
[23]
[18]
[18]
[18]
Ref.
not have any influence on the gas yield [74].
In addition to the gas yield, the composition of the gas is also af-
fected by the use of catalysts. The application of Pt/C catalyst was re-

HHV

−18
−27
226
100
sponsible for a rise in the C2H6 and CH4 content [48]. Ni/SiO2-Al2O3

−9
47
26
36
51
21
22
23

10
9

8
1
and Ru/C catalysts demonstrated a better decarboxylation activity,
particularly in gas fractions. For instance, in the absence of H2, Ni/SiO2-

−10

−44
Al2O3, and Ru/C catalysts supported the production of C2H6, CH4, and

179

140

261
158
9
S

–
–
–
–
–
–
–
H2. On the other hand, when H2 was present, the utilization of the same
catalysts resulted in the production of a high amount of CO2 [83]. The

% change due to catalytic effects on biochar

use of alkali catalysts led to a higher production of CO2, whereas the

−30

−17
−42
−59
−56
−63
−22
−22
−56
−4
61

50
32

58
28
12
application of organic acid-based catalysts resulted in a rise in the

N
amount of H2, CO, and CH4 in gas products [45].

−100

−19
−88
−31
−38
−29
−28
−28
−14
−15
−13

−65
8. Effect of catalyst on HTL biochar

402
−6

−3

13
O
Acid catalysts, including sulphuric acid and acetic acid, had shown
to increase the biochar yield but decrease the bio-oil output [22].

−43
−48
−64
279
92
63
48
28
17

14
20

14
Compared to acetic acid, sulphuric acid generated a higher quantity of

7
0
solid residue [22]. The reduction in the bio-oil yield and rise in the solid
residue was probably the outcome of the polymerization of the hy-

−19
−29
115

−9
drolyzed products under acidic conditions [22].

65
55
43
29
27
14
12
12
C

5
5
4
1
Alkali catalysts are well documented as inhibitors for the char for-
mation [84]. At the same time, these catalysts also helped to improve

HHV

21.8
31.7
25.9
21.4
31.9
25.9
27.8
27.8
27.8
27.8
27.8
27.8
27.8
24.6
21.8
15.1
the production of bio-oil [74,77,85,86]. For instance, the utilization of
K2CO3 dramatically reduced the biochar yield from 42 wt% to 4 wt%

0.6
0.4
0.4
0.3
0.2
0.6

0.2
0.7
0.7
compared to the non-catalytic approach [18]. KOH also helped to re-

S
duce the yield of solid residues from 33 wt% to 12 wt% [45]. The
following section describes the mechanism for alkali-catalyzed reduc- N (%)

2.1
3.3
3.8
2.2
4.6
0.8
0.1
0.1
0.1
0.1
0.1
0.1
0.1
4.8
3.2
2.6
tion in biochar yield. The unsaturated molecules can contribute towards
solid residues via polymerization. An increase in the pH due to the
O (%)

application of alkali catalysts causes monomer dehydration by which

34.8
12.0

13.2
24.9
21.9
21.9
21.9
21.9
21.9
21.9
21.9

12.8
0.0

1.9

2.4
8.5
the production of unsaturated molecules may get inhibited [87]. Hence,
in the alkali catalyzed HTL, the solid residues were found in minimal
H (%)

quantities. The utilization of alkali catalysts further reduces the re-

5.9
9.5
7.8
7.0
9.2
5.0
4.9
4.9
4.9
4.9
4.9
4.9
4.9
6.0
4.4
3.6
Non-catalytic

polymerization and condensation of intermediate compounds, thereby

inhibiting the production of char [88]. In addition, certain organic acids
C (%)

that would generally increase the polymerization were neutralized by

41.5
62.8
55.6
50.2
66.7
68.7
73.1
73.1
73.1
73.1
73.1
73.1
73.1
54.9
43.1
37.4
alkali catalysts [89].
Table 5 shows the % change in the elemental composition and HHV
HHV

15.8
17.7
17.0
23.6
17.2
22.9
22.8
22.6
25.5
25.2
25.8
27.5
27.0
26.5
20.5
6.7

of biochar produced from different biomass due to the addition of

catalysts. A dramatic increase in C and H biochar contents of more than
100 and 200% were observed when Na2CO3 alkali catalyst was used for
Effect of catalyst on the elemental composition of biochar obtained via HTL.

0.0
0.3
0.1
0.0
0.1
0.7

0.4
0.2
0.3
–
–
–
–
–
–
–
S

Isochrysis HTL. However, biochar generated from Pavlova biomass via

the same Na2CO3 has been shown to have reduced C and H content
N (%)

compared with non-catalytic biochar. Similarly, highly contrasting re-

1.3
4.7
2.5
1.7
4.8
1.0
0.1
0.2
0.2
0.2
0.1
0.1
0.2
3.1
2.5
2.3

sults were obtained for O, N, and S, as well as for HHV of biochar from
different biomass but with the same catalyst. The above results imply
O (%)

that the type of biomass and catalyst appears to have an interactive

7.0
7.5
2.5
38.7
37.2
14.9
15.0
19.1
40.2
31.0
30.2
30.2
25.5
25.7
25.2
22.5

effect as far as the biochar composition and HHV are concerned. Few
investigations reported that the loading of a catalyst affects the quality
H (%)

of the char produced. For example, the rise in the dose of the KOH
10.6

10.0
1.6
4.9
4.8
4.7
7.2
4.3
4.7
4.3
4.1
4.5
4.3
4.6
4.9

8.4

catalyst increased the amount of ash but reduced the carbon content of
Catalytic

biochar, thereby decreasing its HHV [23,77].

C (%)

19.3
38.0
35.9
35.3
51.8
53.9
64.2
65.3
65.5
69.8
69.9
70.1
72.4
60.6
53.3
52.8

9. Perspective and challenges

Nannochloropsis
Nannochloropsis
Nannochloropsis

Woody biomass
Woody biomass
Woody biomass
Woody biomass
Woody biomass
Woody biomass
Woody biomass

The selection of catalysts needs to be done based on the following

Barley straw

characteristics: activity, shelf life, stability, and cost [8]. In particular, a

Feedstock

Isochrysis
Isochrysis

Pavlova
Pavlova
Pavlova

catalyst with superior stability, i.e., lower deactivation possibility, is

required during the HTL [30]. The requirement of a higher temperature
and longer residence time resulted into a rise in the cost of HTL. In this
case, the development of a catalyst which can reduce the temperature
Colemanite
HT/KOH

and residence time without compromising the bio-oil yield can improve
Catalyst

Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3

Na2CO3
Na2CO3
Na2CO3
Table 5

K2CO3

K2CO3
FeSO4

the economics of the HTL process.

MgO

KOH
HT

There are several ways in which the quantity, as well as quality of

8
S. Nagappan, et al.
the bio-oil, can be effectively increased.
• A catalyst probably influences one or two reactions in HTL. In this
regard, the use of multiple catalysts together may influence multiple
reactions that lead to the desired target i.e., high bio-oil yield and
better bio-oil quality. Nevertheless, the reaction processes and cat-
alytic mechanisms need to be explored before pursuing the above-
mentioned option.
• The bio-oil content can be improved by inhibiting the formation of
gaseous fractions. Avoiding the use of catalysts like Ni (which are
well known for gasification), can help to prevent the formation of
gas fractions [90].
• Continuous operation of a catalytic HTL is better than a batch pro-
cess because it may give higher yields of bio-oil. But, to date, the
catalytic HTL has primarily been studied in small-scale experiments
in a batch reactor. In addition, the investigations reporting the
commercial-scale testing of HTL are very few [91]. One of the major
limitations allied with continuous operations is the replacement of
catalyst.
• Further work is needed to find an effective heterogeneous catalyst
for HTL [30]. The transition metal-based catalyst as the active in-
gredient can improve the quality of the bio-oil.
In spite of numerous advantages, catalytic HTL poses some pro-
blems which have to be resolved. For instance, even though acid cat-
alysts are known to improve bio-oil production, it is not widely used as
alkali. The reason is that under the acidic conditions, HMF – an inter-
mediate product obtained from hydrolysis of cellulose tends to undergo
polymerization to form undesired char. Consequently, the presence of
char can result in clogging of the reactor lines [28]. Thus inhibiting
solid polymerization using additional catalysts can overcome the above
problem. Another problem that certain catalyst poses is that during
HTL, it leads to higher production of carboxylic acid, which causes
corrosion. In this case, corrosion-resistant materials need to be used for
the construction of the HTL reactor.
Catalyst faces several problems during the service of HTL, which
must also be tackled. For instance, the sulphates and phosphates pre-
sent in the feedstock may promote the catalysts poisoning. But this can
be avoided if a separate precipitation tank is used before HTL. However,
it adds up to the additional capital cost. In another example, excess N2
content in biomass is related to catalytic poisoning. Also, condensation
of the unsaturated compounds and dehydration of the oxygenated
compounds can rapidly deactivate the catalysts. Pre-treatment of bio-
mass to remove problematic substances for catalyst functioning is one
of the promising steps to overcome catalytic poisoning. Nonetheless,
more innovative approaches need to be taken to resolve catalytic poi-
soning.
Another challenge for catalysts during HTL operation is the reuse of
a catalyst, which is very much essential for process economics. Such
reuse options are important, especially in case of the costly metal cat-
alysts. Nevertheless, the loss of catalysts during recycling is very
common in HTL. Studies have also revealed that the use of hetero-
geneous catalysts like Co/Mo/Al2O3, Pt/Al2O3, and others in HTL leads
to metal leaching, which leads to loss of precious catalysts. Therefore,
more importance should be given to the recovery of catalysts in up-
coming studies. Moreover, the process by which the deactivation of a
catalyst occurs has to be explored in detail.
So far, the applications of catalysts have produced mixed results. For
example, Minowa et al. [92] reported an increase in the N2 content
when Na2CO3 was used as a catalyst. In contrast, Yang et al. [93]
documented the denitrogenation of bio-oil using the same catalyst.
Therefore clear effects of catalysts on bio-oil yield have to be estab-
lished. For this to happen, the interactive effect of a catalyst, reaction
parameters, and feedstock composition on the quality of the bio-oil and
other fractions needs to be studied in detail. Besides, a techno-economic
study comparing the catalytic HTL with a non-catalytic HTL is missing
9
Fuel 285 (2021) 119053
from the published literature. Finally, an interpretation of the HTL
catalytic process in detail would be key to the commercialization of
HTL.
10. Conclusion
The yield and physico-chemical properties of bio-oil depend on the
type of catalyst used. Selective catalysts improve the degradation of
polymers, increasing the yield of bio-oil, and reducing biochar output.
The use of catalysts also increases the H/C ratio and minimizes the
hetero-atom content of bio-oil, thereby leading to higher calorific value
and decreased NOx, SOx pollution. So far, the literature pointed out
that the homogeneous class of catalysts, such as KOH and Na2CO3, are
more effective than other heterogeneous catalysts in terms of bio-oil
yield and char reduction. However, the separation or recycling of the
catalyst from the reaction mixture is a major drawback for the homo-
geneous catalyst that needs to be addressed. Future work should con-
centrate on the identification and development of catalysts for HTL
with desirable characteristics, including high-activity (to provide high
yield), high-stability (to withstand HTL operating conditions and to
provide longer lifetime), and low-cost.
CRediT authorship contribution statement
Senthil Nagappan: Methodology, Validation, Writing - original
draft. Rahul R. Bhosale: Conceptualization, Data curation, Project
administration. Dinh Duc Nguyen: Resources, Data curation, Project
administration. Nguyen Thuy Lan Chi: Resources, Data curation.
Vinoth Kumar Ponnusamy: Conceptualization, Writing - review &
editing, Supervision, Funding acquisition. Chang Soon Woong:
Investigation, Supervision, Writing - review & editing. Gopalakrishnan
Kumar: Investigation, Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are thankful to the Ministry of Science and Technology-
Taiwan (MOST107-2113-M-037-007-MY2), and NSYSU-KMU colla-
boration research project (109KN007)-Taiwan for research grant sup-
ports. This work was also financially supported by the Research Center
for Environmental Medicine, Kaohsiung Medical University, Kaohsiung,
Taiwan from The Featured Areas Research Center Program within the
framework of the ‘Higher Education Sprout Project’ by the Ministry of
Education (MOE) in Taiwan. This study is supported partially by
Kaohsiung Medical University Research Center Grant (KMU-
TC108A01). The authors are thankful to Sri Venkateswara College of
Engineering – Sriperumpudur, India, for supporting the work.
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