Chemosphere 283 (2021) 131248

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review on hydrothermal liquefaction aqueous phase as a valuable resource

for biofuels, bio-hydrogen and valuable bio-chemicals recovery
Authilingam Swetha a, Sivakumar ShriVigneshwar a, Kannappan Panchamoorthy Gopinath a,
Ramachandran Sivaramakrishnan b, Rajasree Shanmuganathan c, Jayaseelan Arun d, *
a
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, 603110, Tamil Nadu, India
b
Laboratory of Cyanobacterial Biotechnology, Department of Biochemistry, Faculty of Science, Chulalongkorn University, Bangkok, 10330, Thailand
c
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
d
Center for Waste Management - ‘International Research Centre’, Sathyabama Institute of Science and Technology, Jeppiaar Nagar (OMR), Chennai, 603119, Tamil
Nadu, India

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

Handling Editor: Derek Muir Hydrothermal liquefaction (HTL) of biomass results in the formation of bio-oil, aqueous phase (HTL-AP), bio-
char, and gaseous products. Safer disposal of HTL-AP is difficult on an industrial scale since it comprises low
Keywords: molecular acid compounds. This review provides a comprehensive note on the recent articles published on the
Hydrothermal liquefaction effective usage of HTL-AP for the recovery of valuable compounds. Thermo-chemical and biological processes are
HTL-aqueous phase
the preferred techniques for the recovery of biofuel, platform chemicals from HTL-AP. From this review, it was
Bio-oil
evident that the composition of HTL-AP and product recovery are the integrated pathways, which depend on
Bio-hydrogen
Bio-chemicals each other. Substitute as reaction medium in HTL process, growth medium for algae and microbes are the most
Gasification common mode of reuse and recycle of HTL-AP. Future research is needed to depict the mechanism of HTL process
when HTL-AP is used as a reaction medium on an industrial scale. Need to find a solution for the hindrance in
commercializing HTL process and recovery of value-added compounds from HTL-AP from lab scale to industry
level. Integrated pathways on reuse and HTL-AP recycle helps in reduced environmental concerns and sustain­
able production of bio-products.

1. Introduction biofuel production (Yuan et al., 2019; Alimoradi et al., 2020). This HTL
process is employed on certain rigorous conditions such as temperature
Microalgae are grown in industrial wastewater through mixotrophic (200–400 ◦ C), the residence time of about 15–120 min, and pressure
cultivation that utilizes carbon emissions from the same industry as a (10–25 MPa) (Chen et al., 2018). Since water is used as a reaction me­
source of carbon has an enormous potential to be commercially valo­ dium in the HTL process, there is no necessity for the biomass to be dried
rized into various energy and non-energy related products (Cai et al., (Meng et al., 2017). Emulsification, esterification, pyrolysis and
2019; Chew et al., 2020; Gupta et al., 2021). Fig. 1 Illustrates various hydro-treatment techniques are the other methods utilized for the pro­
such products produced from mixotrophic cultivated microalgal duction of bio-crude oil (Sharifzadeh et al., 2019). After sequential re­
biomass. Microalgae consume the organic pollutants present in the actions (hydrolysis, repolymerization, decarboxylation, and
wastewater, sunlight and carbon dioxide present in the atmosphere for dehydration), the wet biomass is converted into solid residue, gas
bulk biomass production (Mohsenpour et al., 2020; Song et al., 2020; product, bio-oil and HTL-AP with soluble nutrients and organics in it
Yadav et al., 2021). This biomass was converted into biofuels and bio­ (Zheng et al., 2017; Zhang et al., 2019).
char primarily via hydrothermal liquefaction process (Xu et al., 2018; Despite providing useful applications, the HTL process possesses few
Cui et al., 2020). drawbacks such as the formation of aqueous phase (HTL-AP), formation
Hydrothermal liquefaction (HTL) is one of the thermochemical of gaseous products at higher temperatures, tedious cleaning process,
conversion methodologies which has a huge commercial potential for scalability from lab scale to commercialization (Bueno et al., 2020;

* Corresponding author.
E-mail address: arunjayaseelan93@gmail.com (J. Arun).

https://doi.org/10.1016/j.chemosphere.2021.131248
Received 15 October 2020; Received in revised form 10 May 2021; Accepted 14 June 2021
Available online 21 June 2021
0045-6535/© 2021 Elsevier Ltd. All rights reserved.
A. Swetha et al. Chemosphere 283 (2021) 131248

various platforms like Elsevier, Springer and other resources that are
made related to hydrothermal liquefaction of biomass for resource re­
covery. Mainly biofuel recovery was the ideal target of researchers those
are working on thermo chemical processes. Various by-products like
biochar, aqueous phase and gaseous products were recovered from the
process. Currently researchers have changed their view on decoding
applications of biochar. Not many studies were reported on recovering
resource from hydrothermal liquefaction wastewater. Hence this review
will provide economical benefits of hydrothermal liquefaction aqueous
phase via resource recovery like enzymes, platform chemicals, etc.

2. Hydrothermal liquefaction

Hydrothermal liquefaction (HTL), also called hydrous pyrolysis, will

process any kind of biomass such as wet, dry, etc. Hydrous pyrolysis
deals with the de-polymerization process which was carried out in an
enclosed reactor at controlled pressure (10–25 MPa) and temperature
(200–400 ◦ C) (Xue et al., 2016; Yadav and Reddy, 2020). The HTL
process produces liquid bio-crude oil as the primary product, with gas,
aqueous, and solid residue as by-products. Wet biomass can be processed
in HTL, but in the case of pyrolysis, the biomass must be free of moisture
(<5%) (Gulab et al., 2016; Ranganathan and Savithri, 2019). Water is
used as a solvent in the HTL process, as the conditions are towards the
critical point of the water (374 ◦ C and 22 MPa). This change in prop­
erties of water makes it possible to bring about a homogenous, fast and
productive reaction. The subcritical water (374 ◦ C) as a medium plays
an important role in heat transfer and extraction processes (Watson
et al., 2020). The product yield was primarily influenced by the process
conditions (temperature, pressure, reaction time, catalyst, biomass to
solvent ratio and the type of feedstock). There are multiple complex
Fig. 1. Various commercial products that are recovered from microalgae reactions taking place during the HTL process (Gollakota et al., 2018)
biomass cultivated mixotrophically (wastewater and chemical among which, Depolymerisation, decomposition and recombination are
growth medium). the three major steps. Biomass gets disintegrated into several small
compounds by the process of decomposition followed by
Cordova et al., 2020). The amount of aqueous phase formation primarily de-polymerization (Gu et al., 2020). As these separate compounds are
depends upon the biomass to solvent ratio and operating conditions highly unstable, it undergoes recombination to form bio-crude oil, solid
(temperature, time and pressure) used in the HTL process. This waste­ compounds, and gas. Residence time and temperature are the critical
water also accounts for a high concentration of ammonia that is process parameters that define the products (Bio-crude oil, biochar,
1.86–7.07 g/L and also high chemical oxygen demand (COD) of 46–401 gaseous products and aqueous phase) distribution in HTL process.
g/L (Watson et al., 2017). This wastewater is primarily comprised of Carbohydrates, proteins, lipids, lignin, and other complex com­
sugars, acids, ketones, furans, alcohols, N-heterocyclic compounds, and pounds make up the biomass. In HTL process, the biomass initially un­
cyclic hydrocarbon (Madsen et al., 2016). Additionally, due to the dergoes depolymerisation (Dandamudi et al., 2019; Onder et al., 2020;
presence of highly toxic and hazardous elements, it poses a severe threat Sharma et al., 2020). The thermal stability of the biomass was contrib­
to our environment and the living organism (Tommaso et al., 2015). The uted by the hemicellulose and cellulose biopolymers. At a specific
economic viability of the process will be improved by HTL aqueous temperature and pressure the long-chain molecules are converted into
phase recycling or reuse. short-chain hydrocarbons (Fernandez et al., 2018). The second step is
Despite the usage of bio-crude oil, the HTL-AP was also utilized in decomposition, dehydration, decarboxylation, and deamination (Alba
versatile applications such as platform chemicals recovery and reaction et al., 2013). The hydrolysis process converts the macromolecules found
medium in HTL process (Liu et al., 2018). HTL-AP as co-solvent in HTL in wet biomass into monomers and polar oligomers. Breaking down the
process increased the bio-oil yield with a lesser amount of organics hydrogen bond in the complex cellulose molecule produces monomers
penetration into the HTL-AP layer (Biller et al., 2016). Similarly, cata­ like glucose. Glycolaldehyde, phenols, polar organic molecules, and
lytic hydrothermal gasification is another means to valorise HTL-AP organic acids are the main products of this step. The recombination and
(Zhang et al., 2018). Hydrothermal gasification, thermochemical recy­ repolymerization of fragments in the third step. Due to the unavail­
cling, anaerobic fermentation, and several integrated pathways are such ability of the hydrogen compound, the reverse of the initial process
examples that push the fact that the HTL-AP must be reutilized properly occurs in this step (Liu et al., 2018). Coke formation or high molecular
compared to wastewater treatment. Recent studies have also shown that weight char compounds are formed when there is excessive unavail­
HTL-AP treatment produced gas fuels and electricity by the process such ability of solvent (Reddy et al., 2013).
as biological (Si et al., 2019) and biochemical processing (Shen et al., Anastasakis and Ross (2015) investigated the ability of L. Hyperborea,
2018). Despite being advantageous, valorisation has its disadvantage L. digitata, and A. esculenta for biofuel production via HTL process at a
such as inhibition in biological conversion, limited information in the temperature of 350 ◦ C and residence time of 15 min and obtained a
literature regarding the comparison of technical, environmental, and bio-crude yield of 9.8–17.8 wt % individually. The biomasses Nanno­
economic challenges of the various approaches. It is necessary to chloropsis salina and Galdieria sulphuraria resulted in higher bio-oil yield
determine the method by which the energy present within HTL-AP is to (59 wt% and 31 wt%) when processed under subcritical conditions,
be unleashed. temperature between 310 and 350 ◦ C and at a pressure of 1.38 MPa
The idea behind this review was to consolidate all publications in (Cheng et al., 2019). From the previously mentioned studies, it was clear
that bio-oil yield varies based upon the biomass used in HTL process.

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A. Swetha et al. Chemosphere 283 (2021) 131248

Table 1
Literature note on the major compounds detected in HTL-AP of various biomasses.
Algae (Maddi et al., Sludge (Maddi et al., Food waste (Maddi et al., P. juliflora (Arun et al., Pine wood (Panisko et al.,
2016) 2017) 2017) 2019) 2015)

HTL conditions Temperature: 345 ◦ C Temperature: 340 ◦ C Temperature: 340 ◦ C Temperature: 420 ◦ C Temperature: 350 ◦ C
Compounds
Acetic acid 0.56 0.32 0.59 – 0.44
Propanoic acid 0.1 0.05 0.05 – 0.11
2-Butanone 0.03 0.03 0.02 – 0.02
Ethanol 0.12 0.04 1.02 – 0.05
Pyridine 0.08 – – 0.59 –
2-Butanone, – 0.01 0.02 0.42 –
hydroxyl
Pyrazine, methyl 0.04 0.02 0.01 – –
Cyclopentanone 0.008 0.006 0.007 0.20 0.01
Pyrrolidinone 0.08 0.06 0.02 0.01 –
Piperidinone 0.08 0.03 0.01 – –
Phenol – 0.01 0.01 0.16 0.01
Acetamide 0.1 0.11 – – –
Butamide 0.06 – – 1.12 –

Fig. 2. Schematic representation of the hydrothermal liquefaction process and possible routes for valorising by-products (biochar, aqueous phase and gas phase) for
resource recovery.

Biomass composition also plays a vital role in product distribution apart 2.1. Hydrothermal liquefaction-aqueous phase
from HTL operating conditions (temperature, pressure, time, catalyst
load and biomass to solvent ratio). In our previous study, C. vulgaris The wastewater produced as a by-product of the HTL process is
biomass upon liquefaction resulted in a higher bio-oil yield of 29.37 wt% known as HTL-AP. HTL- AP’s chemical oxygen demand (COD) reveals
at temperature of 300 ◦ C and residence time of 60 min (Arun et al., that it is made up of organic compounds. These organic compounds are
2018). Liquefaction of Tetraselmis sp. at a temperature of 350 ◦ C, pres­ used as a source of value-added compounds like platform chemicals. As a
sure of 5–21 MPa and residence time of 30 min resulted in a maximum step ahead, this HTL-AP was explored as a reaction medium in HTL
bio-oil yield of 26.3% (Han et al., 2019). From these literature notes, it process (Chen et al., 2019a; Taghipour et al., 2021), a growth medium
was clear that an increase in reaction temperature increased the biomass for algae (Das et al., 2020) and microbes for biomass recovery. In a
conversion percentage. However, further research is needed in depicting recent study, it was reported that the HTL-AP obtained from algae,
the exact mechanism and hindrance in the commercialization of this manure and sludge had COD of 84.4, 80.5, and 80.8 g/L respectively
study from lab scale to industries. (Watson et al., 2020). HTL-AP valorisation techniques are difficult to
perform practically because most of the bioconversion techniques will
not be able to perform at high organics loading. As an example, in
anaerobic fermentation, about 10 g COD/L of organic loading is

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A. Swetha et al. Chemosphere 283 (2021) 131248

Table 2
Literature survey on the usage of HTL-AP as a growth medium, algae culture conditions and biomass productivity.
Biomass for HTL-AP production HTL Conditions Algae growth conditions in HTL-AP Algae cultivated in HTL- Algae Reference
AP yield

Chlamydomanas reinhardtii Temp: 220-310 ◦ C; Dilution: 140 × ; pH: 7.2–7.4; Temp: Chlamydomanas reinhardtii 1.7 g/L Hognon et al. (2015)
Pressure: 20-10 Mpa; 25 ◦ C; Days: 7; ESC: aeration (air with
Time: 60 min 2% CO2); LS: 24 h illumination
Chlorella sorokiniana Temp: 160 ◦ C; Dilution: 0–30 × ; Temp: 2 or 42 ◦ C; C. Vulgaris 2.11 g/L Chen et al. (2017)
Pressure: 110–115 psi; Days: 10; ESC: aeration (air with 0.5%
Time: 20 min CO2); LS: 12 h on/off illumination
Nanochloropsis sp. Temp: 350 ◦ C; Dilution: 40 × ; pH: 7.0–7.5; Temp: C. Vulgaris 0.84 g/L Li et al. (2017b)
Pressure: 35 Mpa; 26 ◦ C; Days: 12; ESC: no aeration; LS: 12
Time; 30–90 min h on/off illuminations
Ankistrodesmus falcatus; Chlorella Temp: 350 ◦ C; Time; Dilution: 50–1000 × ; Temp: 20 ◦ C; All six microalgae species 50–1000 Godwin et al. (2017)
sorokiniana; Pediastrum duplex; 20 min Days: 18–20; ESC: no aeration; LS: 16 h individually or combined mg/L
Scenedesmus acuminatus; on/18 h off illumination
Green macroalgal blooms Temp: 270 ◦ C; Dilution: 200–600 × ; Days: 14; ESC: Scenedesmus abundans 147 mg/L. Kumar et al. (2019)
Pressure: 4.5 Mpa; aeration (air with 2% CO2); LS: 16 h on/ d
Time; 45 min 18 h off illumination
C. Vulgaris Temp: 300 ◦ C; Time; Dilution: 3.5–52.6 × ; pH: 7.0–7.5; C. Vulgaris 0.67 g/L Zhang et al. (2016)
60 min Temp: 26 ◦ C; Days: 11; ESC: no aeration;
LS: 12 h on/off illuminations
P. tricornutum Temp: 400 ◦ C; Dilution: 25 × ; pH: 7.3–7.5; Days: 33 P. tricornutum 13.4 g/L Bagnoud-Velásquez
Pressure: 20 Mpa ESC: aeration (200 L/h, air with et al. (2015)
2.5–3.5% CO2); LS: 24 h illumination
C. Vulgaris Temp: 523–653 K; Dilution: 50–200 × ; pH: 6.9; Temp: 24- C. Vulgaris 0.159 mg/ Chen et al. (2020)
Time: 3–5 min 26 ◦ C; ESC: no aeration; LS: 24 h L.d
illumination
C. Vulgaris Temp: 523–653 K; Dilution: 25 and 200 × ; pH: 8; Temp: Desmodesmus armaus 0.082 mg/ Chen et al. (2020)
Time: 3–5 min 24-26 ◦ C; ESC: no aeration; LS: 24 h L.d
illumination

Temp: Temperature, LS: Light Source, ESC: External source of carbon.

required (Si et al., 2018) and similarly, it was 1–6 g COD/L in the case of complicated organics distribution and thus there are not many reports
the bio-electrochemical process (Shen et al., 2018). This shows that on the production of the chemicals from HTL-AP of algae yet (Watson
HTL-AP has to be diluted before the bioconversion method. The HTL-AP et al., 2020). The cost for the production of chemicals from the HTL-AP
derived from the lignocellulose biomass comprises the least proportion accounts for about 70% of the chemical price. Thus, more advanced
of nitrogen content 0.8 g/L respectively. Henceforth, the total nitrogen technologies should be introduced for the cost-efficient and sustainable
content of this HTL-AP consisted mainly of organic nitrogen and extraction of chemicals from the HTL-AP.
ammonia (Gu et al., 2020). Table 1 elaborates the composition of Nitrogen, Phosphorus, and Potassium are the three major inorganic
HTL-AP obtained from various biomasses. The composition of HTL-AP compounds found in the HTL-AP. They have a wide range of uses as
shows that it can serve as a platform for various valuable products commercial fertilizers. The major source for the commercially used
(Fig. 2.). The total phosphorous content of HTL-AP was influenced by phosphorus was the geological deposits (Desmidt et al., 2015). Studies
the feedstock composition as well as the method used to separate state that the amount of phosphorus, nitrogen, and potassium present in
HTL-AP from the bio-oil (Li et al., 2017a; Leng et al., 2018). Recently, it the aqueous phase obtained from liquefaction of algae biomass was
was studied that HTL-AP can be used to cultivate C. vulgaris and approximately 1–10, 5–20, and 1–8 g/L (Shakya et al., 2017; Quis­
wild-type Desmodesmus armatus (Chen et al., 2020). In another study, pe-Arpasi et al., 2018; Li et al., 2019). Generally, in Industries, ammonia
value-added products such as β-carotene and other platform chemicals is recovered from the HTL-AP using a method called stripping. Thus
were extracted from the HTL-AP produced from Dunaliella salina upon stripped ammonia can be utilized for the production of fertilizers. A
liquefaction at a temperature of 100–200 ◦ C and reaction time of 60 min recent study states that the air stripping method was preferred to extract
(Pirwitz et al., 2016). 90% of ammonia from HTL-AP (McGinn et al., 2019). Despite all these
technologies and methods for the extraction of nutrients from HTL-AP,
3. Resource recovery from HTL aqueous phase the extraction of potassium from the HTL-AP is still challenging. There
are still a lot of organic and inorganic compounds present in the HTL-AP
3.1. Resource for platform chemicals that needs to be recovered. Thus the technology for the extraction of
organic and inorganic compounds from the HTL-AP must flourish.
The HTL-AP is a potential source for the extraction of a wide variety
of highly useful organic compounds. Monomers of Vinyl acetate can be
produced from the HTL-AP (Rasrendra et al., 2011). In recent years, 3.2. Algae cultivation
there has been a surge in demand for glycolic acid which has very good
cosmetic applications (Vatankhah et al., 2020). It has been found that As the non-renewable sources for the production of fuels are being
the HTL-AP has a high concentration of glycolic acid. Phenol extracted constantly depleted, scientists are looking forward to finding an alter­
from the HTL-AP is a potential source in the petrochemical processes native source for the production of fuel that is renewable and sustainable
that are used for the production of dyes, anti-oxidants, pigments, alkyl (Sivaramakrishnan et al., 2021). Mainly N, P, and K are necessary for a
phosphate, formaldehyde and urea resins, and resol resins (Holladay rich algal growth in a medium (Chew et al., 2020; Wágner et al., 2021).
et al., 2007). HTL-AP of rice straw was utilized for the extraction of As the HTL-AP was rich in these nutrients, they are a very suitable
glucose, acetic acid, cyclopentenone, and monophenol (Lyu et al., medium for the growth of algae (Das et al., 2020). At present, many
2015). HTL-AP was utilized to recover platform chemicals and carbox­ studies have been done on the growth of microalgae in the HTL-AP that
ylic acids (Zhang et al., 2018). The HTL-AP obtained from the algae has a are shown in Table 2. In the majority of the cases, algae are used as the
feed for the HTL process and many reports state that the HTL-AP from

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A. Swetha et al. Chemosphere 283 (2021) 131248

Table 3
Literature survey on the biomass, liquefaction conditions, and impact of HTL-aqueous phase on bio-oil yield and its calorific value.
Biomass used in HTL HTL reaction conditions Recycle Aqueous phase Bio-oil yield after Carbon HHV Energy Reference
process cycle yield (wt%) HTL-AP recycled (wt content (%) (MJ/kg) recovery (%)
%)

Spirulina Temperature: 340 ◦ C, 3 60 35 63 28 – Chen et al. (2019a)

Time: 50min
Scenedesmus Temperature: 300 ◦ C, 2 43.4 wt% 47.91 wt% 81 39.22 – Rajan et al. (2019)
abundans Time: 60min
Chlorella glomerata Temperature: 350 ◦ C, 3 60 wt% 20 wt% – – – Parsa et al. (2018)
Time: 15min
Gracillaria gracilis Temperature: 350 ◦ C, 3 65 22 – – –
Time: 15min
Pomace Temperature: 310 ◦ C, 6 – 28 70 33 52 Deniel et al. (2016)
Time: 15min
C. vulgaris Temperature: 265 ◦ C, 3 – 17–33 70 33 31–58 Ramos-Tercero et al.
Time: 30min (2015)
C. vulgaris Temperature: 275 ◦ C, 4 50 35 68 33 48 Hu et al. (2017)
Time: 50min
Cyanidioschyzon Temperature: 2 16.98 32.35 – – – Muppaneni et al.
merolae 180–300 ◦ C, Time: 30 (2017)
min
Barley straw Temperature: 300 ◦ C, 4 48 36 68 28 – Zhu et al. (2015)
Time: 15 min
Grains Temperature: 300 ◦ C, 10 – 35–49 72 31–36 68–102 Biller et al. (2016)
Time: 15 min

algae has a very good potential to support algal growth. Recent studies obtained from lignocellulosic biomass was used to cultivate Enterobacter
state that the algae uptakes and assimilates the P and N present in the species and it resulted in 9.4 folds in the microbial dry cell weight
HTL-AP. This is due to the fact that it is easy for the microalgae to (Shende et al., 2017). The microbes undergo heterotrophic pathways to
convert ammoniacal nitrogen into amino acids (Alba et al., 2013). From convert the organic constituents present in the HTL-AP more actively
the literature note, it was clear that majorly the HTL-AP was blended when compared to that of algae cultivation. HTL-AP of Nannochloropsis
with water for algae cultivation. This was due to the composition of oculata at varying ratios (10–40 vol%) was utilized for the growth of
HTL-AP, since it has small chain compounds like acids, etc. Effect of E. Coli and Pseudomonas putida. The results showed that the maximum
various parameters such as growth period, aeration and temperature on growth of the microbe was when 20 vol% of the HTL-AP was processed
algae growth in HTL-AP blended growth medium were reported in (Nelson et al., 2013). In HTL-AP, the microbe growth inhibitory com­
literature. Based on the mode of growth/yield quantification, re­ pounds are the aldehydes. These inhibitory compounds damage the
searchers have reported the biomass yield as g/L, mg/L and mg/L. proteins and therefore causing the protein derivatives to get aggregated
d respectively. and misfolded (Jayakody et al., 2018). Modification of Pseudomonas
Chlorella sp. was the most common microalgae cultivated using HTL- putida genome resulted in increased tolerance or acclimatization
AP as a growth medium (Watson et al., 2017). HTL-AP obtained from (200-folds) towards HTL-AP (Jayakody et al., 2018).
Chlamydomonas reinhardtii resulted in 1.7 g/L of algae growth (Hognon
et al., 2015). About 2.11 g/L of C. vulgaris algae biomass was cultivated 3.4. Liquid biofuels
from HTL-AP obtained from liquefaction of Chlorella soroliniana biomass
(Chen et al., 2017). In another study, C. vulgaris biomass was cultivated HTL-AP is a potential resource for enhancing the bio-oil yield in the
from HTL-AP which was obtained from liquefaction of Nanochloropsis sp. thermochemical conversion process (Chen et al., 2019a; Jiang et al.,
at 350 ◦ C and 35 MPa. In this study, the researchers obtained an algal 2020). The HTL-AP was also utilized in a mixture with the existing
biomass yield of 0.84 g/L (Li et al., 2017b). HTL-AP obtained from solvent system into the HTL reactor to enhance the yield of bio-oil.
Phaeodactylum tricornutum at a temperature and pressure of 400 ◦ C and Table 3 elaborates the broad literature survey for liquid biofuels pro­
200 bar was utilized as a culture medium for the cultivation of duction from HTL-AP. Recycling of HTL-AP six times resulted in a bio-oil
P. tricornutum and it resulted in 13.4 g/L of biomass yield (Zhang et al., yield increase of 15.1% when compared to that of utilizing freshwater at
2016). Despite the fact that the algae cultivation in the HTL-AP is un­ a temperature of 350 ◦ C for a reaction time of 20 min (Biller et al., 2016).
complicated, there are some challenges in it. The first one is the presence HTL-AP recycle as reaction medium increased crude oil formation from
of organic and heavy metals in the HTL-AP (Leng et al., 2018). A large 14% to 42% for six consecutive cycles at a temperature of 240 ◦ C
quantity of freshwater consumption makes the process economically (Ramos-Tercero et al., 2015). In another study, recycle of HTL-AP ob­
inapt. In order to overcome these issues, many alternative methods like tained from Gracilaria gracillis and Cladophora glomerata resulted in a
the incorporation of low-strength wastewater (Zhou et al., 2013), acti­ maximum bio-oil yield of 16–25% and 17–25% at third cycle respec­
vated carbon (Erkelens et al., 2015), and zeolites (Wang et al., 2019) tively at a temperature of 350 ◦ C for a reaction time of 15 min (Parsa
were studied. et al., 2018). Recycling of C. vulgaris HTL-AP at the fourth cycle resulted
in a maximum of 29–39% of bio-oil yield at a temperature of 275 ◦ C for a
3.3. Microbe cultivation time of 50 min (Hu et al., 2017). Recycle of HTL-AP obtained from the
HTL of Spirulina plantesis at a temperature of 340 ◦ C and time of 50 min
Another potential use of the HTL-AP is that it can be utilized as a showed a bio-oil yield of 30–40% at third cycle (Chen et al., 2019a).
growth medium for cultivating microbial organisms for the recovery of HTL-AP has the potential to improve the footprint and economics of the
value-added chemicals and biofuels. Recently, HTL-AP obtained from liquefaction process (Jensen et al., 2017). It was seen that the presence
loblolly pine and marine Tetraselmis algae were used for the cultivation of low molecular compounds enhances biomass degradation during the
of Rhodococcus opacus and R. jostii. After 11 days, the R. jostii reduced the HTL process. This methodology of recycling the HTL-AP will be a
COD up to 93.4%, and R. opacus promoted the lipid accumulation of promising technique because it is cost-efficient, easy to incorporate, and
about 0.43 g/g cell dry weight (He et al., 2017). Similarly, the HTL-AP comparatively simpler to scale up. This process of recycling the HTL-AP

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A. Swetha et al. Chemosphere 283 (2021) 131248

Table 4 due to negative effects on microbes growth (Fernandez et al., 2018).

Various techniques that are preferred for the pre-treatment of HTL-AP before Methanation has many benefits, including the production of biogas, the
methanation and gasification. reduction of greenhouse gas emissions, and the production of organic
Technique Mode Advantage References manure (Paolini et al., 2018). Hydrolysis, Acidogenesis, Acetogenesis,
Partial Ozone, H2O2, and UV are Biodegradable Quispe-Arpasi
and methanogenesis are the four primary steps in the anaerobic diges­
oxidation preferred to oxidize the products are et al. (2018) tion (AD) method, and the step that limits the rate of the process is
aromatic compounds achieved methanogenesis (Anukam et al., 2019). This technique of valorising the
Extraction Nanofiltration, struvite, Inhibiting Shakya et al. HTL-AP for the production of methane is a very good alternative for
and resin formation to compounds are (2017)
many other fuels obtained from non-renewable resources and is sus­
extract organic and extracted
inorganics from HTL-AP tainable, eco-friendly, and cost-efficient.
Adsorption Activated carbon and Inhibiting Li et al. (2019)
zeolite preferred to adsorb compounds are 3.5.2. Gasification
organics and inorganics removed Gasification is a process where carbon-rich feedstock is partially
from HTL-AP
oxidized by supplying limited oxygen or steam, at a temperature in the
range of about 100–1000 ◦ C to produce syngas. Syngas is a gaseous
as a reaction medium has potential economic implications as in the mixture that contains mainly CO, CO2, CH4, and H2 (Raheem et al.,
coming years there might be a surge in the price of water commodity 2018). This technology is utilized to make use of the trapped organic
(Hu et al., 2017). Thus, in conclusion, this technique of valorising the matter in the HTL-AP. The hydrogen yield from HTL-AP through the
HTL-AP has great potential and is a very suitable method for enhancing gasification process is detailed in Table 6. Gasification of HTL-AP in
the properties of bio-crude oil and energy efficiency. Among all the other 600 ◦ C and 120 min resulted in a hydrogen yield of 21–58% (Duan et al.,
methods of valorising the HTL-AP, this method is very close to reaching 2018). The inorganic compounds in HTL-AP act as a catalyst in the
the commercialization at full-scale. gasification process and thus enhancing the gasification efficiency and
hydrogen production. HTL-AP of C. vulgaris under controlled conditions
3.5. Gaseous fuels in the gasification process produced hydrogen of 3.31–23.65 mg/L, with
the loading of 11,000 mg/L to 2000 mg/L (Cherad et al., 2016). HTL-AP
3.5.1. Methanation processed via gasification process can result in reduced COD and TOC
Various wastewater streams such as cosmetic wastewater (Puyol (Total Organic Carbon) value to a greater extent. From the literature
et al., 2011), olive mill wastewater (Gonçalves et al., 2012), and coal note, it was seen that the higher temperature of gasification resulted in
gasification wastewater (Zhao and Liu, 2016) have been utilized for more amount of syngas formation. The biomass initially undergoes
methane production in past. The effect of algae growth inhibitors (or­ multiple reactions like water gas shift, methanation, steam reforming,
ganics and heavy metals) in the HTL-AP can be reduced by appropriate etc. By water gas shift reaction or low range liquid hydrocarbon via
pre-treatment techniques as mentioned in Table 4. The addition of Fisher-Tropsch synthesis, the additionally produced syngas can be
activated carbon resulted in a 13–298% increase in methane yield with a converted into hydrogen (Raheem et al., 2017).
shorter lag phase. Table 5 shows a literature review on valorising
HTL-AP in the anaerobic digestion process to produce useful methane. In 4. Value addition of algae biomass cultivated from HTL-AP
one analysis, HTL-AP with a volume of 20–40% was mixed with manure
to produce methane with 244–313 mL/g COD via anaerobic digestion Algae is a valuable resource for recovering high-value products.
(Fernandez et al., 2018). In this process of utilizing HTL-AP, microbes Plant biostimulants include phytohormones, polymers, and small mol­
play a significant role. At present, we do not have many studies on the ecules. These biostimulants can improve crop production while also
effect of microbes on the AD of HTL-AP (Si et al., 2019). The organic protecting it from abiotic stresses. These biostimulants are being
compounds present in the HTL-AP increased the syngas formation by researched using wild-type microalgae as a source. Biostimulants-based
enhancing the degradation of the substrate. In the anaerobic digesters, microalgae are still in the research stage; further research is required to
the HTL-AP was mixed in proportion to the amount of waste substrate determine commercial applications. Terpenoids, the largest class of
used. Interestingly, it was also reported that the composition of HTL-AP products that comprises a countless number of bioactive secondary
possess can affect the methanogenic activity in the anaerobic digester metabolites synthesized by plants. These have many applications such as

Table 5
Comparison of pre-treatment steps on HTL-AP for anaerobic digestion of HTL-AP for green fuel (methane) production.
Feedstock for HTL Condition for Anaerobic digestion Pre-treatment Methane yield Energy Outcomes References
HTL HTL-AP generation conditions of HTL-AP (mL/g COD) recovery

Spirulina Temp.: 300 ◦ C; Temp.: 37 ◦ C; Load: Zeolite: 2 g/L 227 65 Increased methane production rate Zheng et al.
Time: 30 min 5 g/L, dilution: 15x (2017)
Chlorella – Temp.: 37 ◦ C; Co-digestion 14–244 – 30% of HTL-AP can be digested but Fernandez et al.
dilution: 5x chloride salts and nitrogen compounds (2018)
Testraselmis – Temp.: 37 ◦ C; Co-digestion 31–133 – exhibit inhibition effects
dilution: 1.67–5x
Nannochloropsis Temp.: 320 ◦ C; Temp.: 37 ◦ C; Load: Struvite 182 52 Greater methane yield with less lag Shakya et al.
Time: 30 min 1 g/L, dilution: 97x recovery phase (2017)
Nannochloropsis Temp.: 320 ◦ C; Temp.: 37 ◦ C; Load: Glacial acetic 84 24 Greater methane yield with less lag Shanmugam
Time: 30 min 1 g/L, dilution: 97x acid: 30% phase et al. (2017)
Corn straw Temp.: 260 ◦ C; Temp.: 37 ◦ C; Load: Nil 156 45 Degradation of furan and nitrogen Si et al. (2018)
Time: 10 min 8 g/L, dilution: 5x compounds to a greater extent
Sewage sludge Temp.: 170–320 ◦ C; Temp.: 37 ◦ C; Load: Nil 136–286 39–81 HTL-AP retention time inversely Chen et al.
Time: 30 min 0.75 g/L proportional to methane yield (2019b)
Swine manure Temp.: 270 ◦ C; Temp.: 37 ◦ C; Load: Glacial acetic 212 61 Increase in methane production rate Si et al. (2019)
Time: 60 min 20 g/L, dilution: 2x acid: 20 g/L and yield with less lag phase
Swine manure – Temp.: 37 ◦ C; Load: Acetic acid: 2 150–175 43–50 Increased methane production rate Zhou et al.
13 g/L, dilution:30x g/L with fewer lag phase (2015)

6
A. Swetha et al. Chemosphere 283 (2021) 131248

Table 6 glucose, cellulose, and starch are present in microalgae biomass. The
Literature note on usage of HTL-AP as resource for valuable hydrogen and polysaccharides (Starch and Glucose) that are extracted from microalgae
methane production via gasification process (Cherad et al., 2016; Duan et al., are utilized for bioethanol and biohydrogen production (Chochois et al.,
2018). 2009). The carbohydrates that are extracted from the microalgae can be
Feedstock for HTL Gasification CH4 H2 TOCr/ utilized in the pharmaceutical industries (Chew et al., 2017), biofuel
HTL Condition for conditions (Vol. (Vol. CODr production (Markou et al., 2012), textile industries, food industries, and
HTL-AP %) %) (%)
in the production of thickening agents, water-soluble lubricants, stabi­
generation
lizers, thickeners, clinical drugs and emulsifiers (Arad and
Nannochloropsis Temp.: 350 Temp.: 600 ± 36 34 84.36 Levy-Ontman, 2010).
oceanica ± 2 ◦ C; 5 ◦ C; Pressure:
Pressure: 30–50 Mpa;
15–18 Mpa; Reaction time: 4.1. Valuable enzymes from algae biomass
Retention 120 min
Time: 60 min Enzymes are essential compounds that play a major role in the re­
Auxenochlorella Temp.: 350 Temp.: 600 ± 37 28 70.61
actions, scaling, and optimization of processes. Enzymes are, in reality,
pyrenoidosa ± 2 ◦ C; 5 ◦ C; Pressure:
Pressure: 30–50 Mpa; the most competent candidate for the majority of industrial processes.
15–18 Mpa; Reaction time: The demand for efficient enzymes to improve industrial processes is
Retention 120 min currently on the rise. As a result, a lot of research is being conducted to
Time: 60 min find a renewable source. Among many other sources, one of the potential
Arthrospira Temp.: 350 Temp.: 600 ± 32 30 94.4
platensis ± 2 ◦ C; 5 ◦ C; Pressure:
sources for enzyme synthesis is algae biomass. In literature, the valuable
Pressure: 30–50 Mpa; Δ6-Desaturase enzyme was extracted from Phaeodactylum tricornutum
15–18 Mpa; Reaction time: microalgae (Zhu et al., 2017). Similarly, various enzymes such as
Retention 120 min acetyl-CoA, acyl-CoA diacylglycerol acyltransferase 1, photo­
Time: 60 min
decarboxylase, glucose-6-phosphate dehydrogenase, and phospholipase
Schizochytrium Temp.: 350 Temp.: 600 ± 35 28 92.64
limacinum ± 2 ◦ C; 5 ◦ C; Pressure: A2 are produced from Chlamydomonas reinhardtii, Chlorella ellipsoidea,
Pressure: 30–50 Mpa; Chlorella variabilis, Phaeodactylum tricornutum, Chlamydomonas rein­
15–18 Mpa; Reaction time: hardtii (Guo et al., 2017; Sorigué et al., 2017; Xue et al., 2017; Rengel
Retention 120 min et al., 2018; Shin et al., 2019). In addition to this, many more in­
Time: 60 min
Ulva prolifera Temp.: 350 Temp.: 600 ± 36 28 57.14
vestigations have been done on the extraction of many valuable enzymes
± 2 ◦ C; 5 ◦ C; Pressure: from the microalgae and among which, few are detailed in Table 7.
Pressure: 30–50 Mpa;
15–18 Mpa; Reaction time: 5. Challenges and future prospects
Retention 120 min
Time: 60 min
Saccharina Temp.: 350 Temp.: 600 ± 29 31 92.22 It is transparent that HTL could process any type of biomass to
japonica ± 2 ◦ C; 5 ◦ C; Pressure: recover various valuable products. HTL-AP can be a vital candidate for
Pressure: 30–50 Mpa; producing value-added chemicals, fuels, and electric gases. The major
15–18 Mpa; Reaction time: outcomes of the review were elaborated on in Table 8. There are many
Retention 120 min
Time: 60 min
feasible approaches for the conversion of HTL-AP, each of which has its
Zostera marina Temp.: 350 Temp.: 600 ± 27 34 66.74 pros and cons. This section explicates the summary of the limitations and
± 2 ◦ C; 5 ◦ C; Pressure: advantages of all the processes studied. The HTL-AP, which has a simple
Pressure: 30–50 Mpa; composition, has been the subject of recent studies. Indeed, shifting the
15–18 Mpa; Reaction time:
study’s focus to treating the HTL-AP with a complex composition would
Retention 120 min
Time: 60 min increase the chances of recovering several more useful products. Addi­
Gracilaria Temp.: 350 Temp.: 600 ± 26 21 86.61 tionally, it also encounters the problem of sustainability and economic
eucheumoides ± 2 ◦ C; 5 ◦ C; Pressure: barrier. On the other hand, separation of HLT-AP after HTL process and
Pressure: 30–50 Mpa; converting it into valuable products using biological methods have great
15–18 Mpa; Reaction time:
Retention 120 min
potentiality in near future. Algae biomass can be cultivated in HTL-AP
Time: 60 min but it may not be as comparable with other chemical mediums. This
Chlorella vulgaris Temp.: Temp.: 350 ◦ C; 20–23 38–71 56–99 was due to the growth inhibition of certain compounds present in the
350 ◦ C; Ambient HTL-AP. Hence these inhibitory compounds must be processed to
Ambient Pressure;
enhance biomass yield. In terms of cost and efficiency, still, further
Pressure; Retention
Retention Time: 60 min investigation is needed for this technique to prosper at a large-scale
Time: 0–60 level. The anaerobic technique also serves a good purpose in terms of
min commercial application. However, the conversion of organics with ni­
trogen is poor and the residual effluent should be treated again by any
other valorisation techniques. Further, the functional microbes must be
biofuels, cosmetics, nutraceuticals, and pharmaceuticals (Vickers et al.,
enriched prior to treatment, and to enhance anaerobic fermentation,
2017). Plants typically produce just a trace amount of these secondary
bio-augmentation must be conducted. Recycling can be employed in
metabolites, so using genetically modified microalgae, these secondary
valorisation techniques such as gasification, liquefaction, etc. to reduce
metabolites may be formed in large quantities and concentrations
operational costs. Gasification is a crucial technique, but it requires a
(Vavitsas et al., 2018; Lauersen, 2019). The three major steps involved
large amount of input energy, catalyst, and high reactor conditions.
in the production of value-added products from algae is harvesting,
Although gasification can be incorporated on a large scale, there are
extraction, and purification. Traditional extraction techniques include
many complications in decoding the reaction mechanism and pathways.
mechanical methods such as mixing and bead beating, ultrasound, and
high-pressure homogenization, as well as chemical methods such as
6. Conclusion
solvent extraction. Microalgae biomass contains carbohydrates of 50%
of its dry matter. Monosaccharides such as fructose, galactose, manose,
To conclude, this review analyses the biological and chemical

7
A. Swetha et al. Chemosphere 283 (2021) 131248

Table 7
Valuable enzymes that are recovered from the algal biomass that was cultivated from HTL-AP (Rodríguez-Jasso et al., 2013; Trivedi et al., 2015; Vermaas et al., 2015;
Parab et al., 2017; Kang et al., 2018).
Algae Type of Algae Technique Micro-organism used Enzyme produced

Fucus vesiculosus Brown Algae Solid-State Fermentation Aspergillus niger & Mucor sp. Fucoidanases
Ulva fasciata Green Algae Solid-State Fermentation Cladosporium sphaerospermum Cellulases
Saccharina japonica Brown Algae Submerged Fermentation Defluviitalea phaphyphila sp. Alginate lyases
Gigartina skottsbergii Red Algae – Pseudoalteromonas carrageenovora κ-Carrageenases, and ι-Carrageenases
Gracilaria verrucosa Red Algae Submerged Fermentation E. coli, Pseudoalteromonas sp. and galactanivorans sp. Agarase, neoagarobiose hydrolase and carrageenase
Sargassum sp. Brown Algae Submerged Fermentation Bacillus sp. Laminarases
Ulva lactuca Green Algae Solid-State Fermentation Bacillus sp. Xylanases
Padina tetrastromatica Brown Algae Solid-State Fermentation Bacillus sp. Xylanases
Ahnfeltia plicata Red Algae Solid-State Fermentation Bacillus sp. Xylanases
Gelidium amansii Red Algae Submerged Fermentation Raoultella ornithinolytica 3,6-Anhydro-Lgalactose dehydrogenase

techniques for the valorisation of HTL-AP that was ended up as a by-

Table 8 product from HTL of biomass. To start with, the review was focused to
Outcomes of this review and applications of HTL-AP for valuable products depict the characteristics of HTL-AP for reuse and recycle. This review
recovery. also comprises pathways for value addition of HTL-AP via algae culti­
Technique for Description Advantages Dis-advantages vation, microbe cultivation, biofuel production, green fuel production.
valorising the Further, it has been suggested that more focus has to be brought on HTL-
HTL-AP
AP and try to make the process energy-efficient, economical with less
Algae Algae is cultivated 1.) The produced 1.) Only limited environmental impacts. Therefore, the integrated models possess a
cultivation in HTL-AP, as it biomass will serve organics get promising potential for HTL-AP valorisation.
contains nutrients as a raw material converted and
and organics for its for the production heavy dilution is
sustainable of platform necessary Credit author contribution statement
growth. In biochemicals and
addition, carbon is fuels
Authilingam Swetha: Conceptualization, writing- original draft.
captured by the 2.) Efficient 2.) Accumulation
biomass recovery of of heavy metals in Sivakumar ShriVigneshwar: writing-original draft. Kannappan Pan­
nutrients from biomass chamoorthy Gopinath: Supervision, writing – review & editing.
HTL-AP Ramachandran Sivaramakrishnan: Supervision, writing – review &
Methanation Organics in the 1.) Efficient 1.) Retention time
editing. Rajasree Shanmuganathan: writing – review & editing.
(Anaerobic HTL-AP are conversion of is long and dilution
Digestion) converted into organics and less is necessary
Jayaseelan Arun: Supervision, project administration, Writing - review
methane and production of & editing.
hydrogen by an sludge
anaerobic 2.) Alternative for 2.) Removal of
digestion method many fossil fuels limited nutrients
Declaration of competing interest
and operating cost
is less.
Hydrothermal Gasification is a 1.) Efficient and 1.) Catalysts are The authors declare that they have no known competing financial
gasification process in which fast conversion of required and the interests or personal relationships that could have appeared to influence
carbon-rich the organics to operating
the work reported in this paper.
feedstock is syngas temperature and
partially oxidized pressures are high
in presence of 2.) Dilution is not 2.) Nutrient Acknowledgement
limited oxygen required and removal is limited
supply or air of valuable green
steam at a fuel is produced
Authors wish to acknowledge www.freepik.com for the resource of
temperature in the diagrams. Also, wish to thank SSN college of Engineering and Sathya­
range of about bama Institute of Science and Technology for the support.
100–1000 ◦ C to
produce syngas.
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