Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

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Renewable and Sustainable Energy Reviews

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A review on hydrothermal liquefaction of biomass

⁎ ⁎
A.R.K. Gollakotaa, Nanda Kishoreb, , Sai Gua,
a
Department of Chemical and Processing Engineering, University of Surrey, Guildford GU2 7XH, United Kingdom
b
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Assam 781039, India

A R T I C L E I N F O A BS T RAC T

Keywords: The rapid depletion of conventional fossil fuels and day-by-day growth of environmental pollution due to
Wet biomass extensive use of fossil fuels have raised concerns over the use of the fossil fuels; and thus search for alternate
Dry biomass renewable and sustainable sources for fuels has started in the last few decades. In this context biomass derived
Hydrothermal liquefaction fuels seems to be the promising path; and various routes are available for the biomass processing such as
HTL mechanism
pyrolysis, transesterification, hydrothermal liquefaction, steam reforming, etc.; and the hydrothermal liquefac-
Value-added chemicals
tion (HTL) of wet biomass seems to be the promising route. Therefore, this article briefly enlightened a few
Energy efficiency
concepts of HTL such as the elemental composition of bio-crude obtained by HTL, different types of feedstock
adopted for HTL, mechanism of HTL processes, possible process flow diagrams for HTL of both wet and dry
biomass and energy efficiency of the process. In addition, this article also enlisted possible future research scope
for concerned researchers and a few of them are setting up HTL plant suitable for both wet and dry biomass
feedstock; analyzing influence of parameters such as temperature, pressure, residence time, catalytic effects,
etc.; deriving optimized pathways for better conversion; and development of theoretical models representing the
process to the best possible accuracy depending on nature of feedstock.

1. Introduction production by pyrolysis of lignocellulose biomass. Several statistics

The rapid increase in energy demand and the lack in the supply to
cater the needs, enables to find the alternatives to meet the current
demands of the society which is of primary concern in terms of socio
economics of the globe. The rapid growth rate of urbanization in the
past decades, water quality degradation became a public health threat.
Eutrophication associated with nutrient content of wastewater and
treatment plant effluents have become a serious concern to water
environment. Combining these two critical environmental and social
causes an alternate source for the conventional fossil fuels which has to
be sustainable, energy secured, and reduce global warming is highly
desirable. This lead several researchers to focus in search of alternate
source for commercialization from several decades and came up with
one source which is nothing other than the biomass. Biomass sources
include wood wastes, energy crops, aquatic plants, agricultural crops,
and their waste products and municipal and animal wastes; and are
considered as potential sources of fuels and chemical feedstock's. The
choice of biomass and its derivatives generate high expectations for the
production of fuels, raw materials for synthesis in the petrochemical
industry and fine chemicals. Biomass, in addition to the production of
the first generation biofuels (bioethanol and biodiesel), is also of
interest for the production of bio oil due to its perspectives for
related to production and consumption of biomass as an alternated
source of energy is listed by several authors. As of 2010, world biofuel
production has been largely focused on first generation bio fuels
producing ethanol and biodiesel from starch, sugars, and vegetable
oils. Advanced bio fuels or biofuels produced from lignocellulose
materials such as wood waste and straw made up to only 0.2% of total
biofuel production. In recent years, research on using biomass for
liquid fuels has been robust, ranging from studies of pyrolysis and
hydrothermal liquefaction (HTL) of lignocellulose material, gasification
and biomass to liquid technologies to the upgrading processes.
Secondly, converting biomass from its natural solid form to liquid
fuels is not a spontaneous process. The liquid fuels that humans have
harnessed on a large scale as fossil fuel took thousands of years of
geochemical processing to convert biomass to crude oil and gas. In
recent years, several conversion technologies have been developed to
obtain liquid products from different kinds of biomass for use as fuels
and chemicals. Biomass conversion technologies are broadly classified
into two categories namely, biochemical and thermo- chemical con-
version. In general, the unprocessed bio-oil derived from the biomass
has low energy density, high moisture content, and its physical form is
not free flowing that creates a problem as a feedstock for reciprocating
engines. Thermochemical conversions compared to biochemical con-

⁎
Corresponding author.
E-mail addresses: nkishore@iitg.ernet.in (N. Kishore), sai.gu@surrey.ac.uk (S. Gu).

http://dx.doi.org/10.1016/j.rser.2017.05.178
Received 14 August 2016; Received in revised form 26 April 2017; Accepted 20 May 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Gollakota, A.R., Renewable and Sustainable Energy Reviews (2017), http://dx.doi.org/10.1016/j.rser.2017.05.178
A.R.K. Gollakota et al.
versions are processed at several higher degrees of temperature in the
presence of appropriate catalysts to obtain liquid products from
different sources. In general, thermochemical conversions are much
rapid than the biochemical conversions. Thermochemical conversion
conversions generally implied to upgrade biomass by heating under
pressurized and oxygen deprived enclosure. It can be further classified
into combustion, gasification, pyrolysis, and direct liquefaction. Among
which direct liquefaction or hydrothermal liquefaction is one of the
promising routes that drawn attention in the recent past. This process
is synonym of hydrous pyrolysis, but compared to pyrolysis HTL is
carried at lower temperatures and heating rates. In other words,
hydrothermal liquefaction of biomass is the thermochemical conver-
sion of biomass into liquid fuels by processing in a hot, pressurized
water environment for sufficient time to break down the solid bio
polymeric structure to mainly liquid components. Typical hydrother-
mal processing conditions are 523–647 K of temperature and operat-
ing pressures from 4 to 22 MPa. The low operating temperature, high
energy efficiency and low tar yield compared to pyrolysis is the key
parameter that drives the attention of researchers on the liquefaction
process.
Till date all the paradigm research on the production of biofuel is
rested on the solid dry wood but liquid bio-waste has a better edge over
the solid manure which is the critical processing parameter for the
hydrothermal liquefaction process. Among several possibilities of wet
biomass, microalgae is considered to be an excellent source of biofuel
production because of their advantages such as high photosynthetic
efficiency, maximum biomass production, fast growth rate and lack of
arable soil requirements. A very little attention on the HTL of wet
biomass process is available as of now and very few attempts of pilot
plants globally, for instance, Pittsburgh Energy Research centre of U.S
Bureau of Mines took place in 1990s but stopped later on due to
economic crisis. Hence, an attempt has been made to bridge the gap in
the literature and create a possibility to take the research on HTL of
biomass to next level by selecting the best available feedstock and the
operating conditions. Further research on tuning of the critical
operating parameters like temperature and pressure for better yield
is still under progress. Thus, this article tries to enlighten the existing
knowledge and research gaps available pertained to biomass and
hydrothermal liquefaction. However, before presenting thorough lit-
erature review along with HTL mechanisms, energy efficiency and
advantages/disadvantages of this process, a few details of elemental
composition; and wet and dry biomass feedstock suitable for HTL are
presented below.
1.1. Elemental composition of biomass
Any biomass consists of elemental carbon (C), hydrogen (H),
nitrogen (N), sulphur (S) and oxygen (O); and a few details of them
are presented below.
1.1.1. Carbon (C)
It is obviously the most important constituent of the biomass. It
comes from the atmospheric CO2 that become a part of the plant
matter during photosynthesis. Carbon represents the major contribu-
tion to the overall heating value. During combustion, it is principally
remodelled into CO2 that is discharged within the atmosphere [1]. In
any combustion application an area of carbon is not combusted utterly
and ends up in emissions of change state gases, usually carbon-
monoxide gas or PAH's [2]. Generally, the carbon content of the fuel
is estimated via the composition of lignin, hemicellulose and cellulose.
Similarly, the char content is majorly depended on the amount of the
lignin i.e., for herbaceous biomass yields lower carbon content as
compared to wood biomass. Fuels rich in lignin, such as olive kernel,
have carbon contents higher than 50% (by wt) on dry basis [3].
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Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
1.1.2. Hydrogen (H)
It is another major constituent of biomass, as can be expected from
the chemical structure of the carbohydrate and phenolic polymers.
During combustion, hydrogen is converted to H2O, significantly
contributing to the overall heating value [4]. The weight content of
hydrogen, on a dry basis, is usually slightly lower in herbaceous
biomass (5.5–6%) than in woody biomass (6–8%) [3].
1.1.3. Nitrogen (N)
It constitutes the vital nutrient form for plants. For instance, the
nitrogen is applied as a fertilizer to soil that enhances the growth and
yield of the plants. By the continual application of the nitrogen in the
modern day agricultural era, the nitrogen content of herbaceous
biomass species acquires a greater amount of nitrogen ranging between
(0.4–1.0% wt dry basis) compared to woody biomass [5]. Further, the
presence of nitrogen significantly contributes the degradation in
biochemical processes like digestion or fermentation. On the other
hand, nitrogen during combustion process doesn’t oxidize and there-
fore its contribution to the overall heating values [3].
1.1.4. Sulphur (S)
This is considered to be the other important nutrient hindered in
structures of amino acids, proteins and enzymes for substantial plant
growth similar to nitrogen. The high growth rate of most herbaceous
crops means that the sulphur concentration in plant biomass is
typically higher than those in woody biomass. The concentration of
sulphur in wood can be as low as 0% (which means below the detection
limit of most laboratory devices) and reaches up to 0.1% on a dry basis
in exceptional cases, herbaceous biomasses have a sulphur content
ranging from 0% to 0.2% or even higher [6]. In waste fractions, values
up to approximately 1% have been reported. However, it's most
important impact relates to gaseous emissions, syngas cleaning in
gasification processes and corrosion [3].
1.1.5. Oxygen (O)
Oxygen constitutes the vital element in the chemical composition of
the biomass which is evident from the nature through photosynthetic
process. The composition of the oxygen content controls the heating
value of the bio crude that is obtained via any processing technique [7];
and majority of the bio crudes are limited their utilization just because
of the excess content of the oxygen. It is evident that the oxygen content
in the phenolic compound structure are very complex to break (or to
remove) it in the form of water so that to enhance the heating values. It
should be noted that oxygen is not measured directly – its weight
concentration is estimated by subtracting from 100 the concentrations
of all other elements (C, H, N, S) and of the ash content in the dry fuel
[3]. In the context of HTL of biomass, the elemental composition of
bio-crude obtained by the hydrothermal liquefaction of both wet and
dry biomass is given in Table 1.
1.2. Biomass Feedstock
1.2.1. Dry feedstock
The tangled biomass properties lead to the braid chemical reactions
during the hydrothermal liquefaction procedure. Woody biomass/
lignocellulose built is embedded with hemicellulose, cellulose and the
lignin compounds; and hence the rigid crystallinity of the structure
makes it rigid and tougher to process. Further, accommodating a
continuous flow framework again involves the complexity of the
procedure that leads to the solubility criteria in the solvents due to
the hindered resistance to the structure of biomass. Thus the entire
framework of the process is penalized economically. Despite, the
intrinsic source of hydrogen and carbon, the processing of the
lignocellulose biomass is limited due to the substantial amount of the
oxygen. The detailed explanation of the individual fractions of ligno-
cellulose is presented below.
A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Table 1
Elemental composition of the bio crude obtained through hydrothermal liquefaction of biomass (both wet and dry).

S.No Feedstock Elemental composition of product species after HTL References

C (%) H (%) N (%) O (%) S (%) Ash (%) Moisture (%) HHV % Yield

1 Spirulina algae 68.9 8.9 6.5 14.9 0.86 – – 33.2 32.6 Vardon et al. [8]
2 Swine manure 71.2 9.5 3.7 15.6 0.12 – – 34.7 30.2
3 Anaerobic sludge 66.6 9.2 4.3 18.9 0.97 – – 32.0 9.4
4 Arthrospira platensis 74.5 10.2 6.8 7.5 1.0 – – 38.65 30 Lavanya et al. [9]
5 Tetraselmis 71.4 9.5 5.7 12.3 1.1 – – 35.58 29
6 Nannochloropsis gaditana 76.1 10.3 4.5 8.8 0.4 – – 38.00 Barriero et al. [10]
7 Scenedesmus almeriensis 74.9 9.1 5.9 9.6 0.7 – – 36.20
8 Nannochloropsis Sp 77.2 9.9 4.7 8.2 0.5 – – 39
9 Almeriansis 73.2 9.3 5.1 0.8 11.7 35.8 20.0 – 42.6
10 Gaditana 74.2 9.3 4.0 0.6 11.8 36.2 12.4 – 50.8
11 Nannochloropsis Oceana 77.6 4.9 3.4 – 0.3 – – 37.70 54.2 Caporgno et al. [11]
12 Derbesia 73 7.5 6.5 10.6 0.7 – – 33.2 Neveux et al. [12]
13 Ulva 72.6 8.2 5.8 11.0 0.4 – – 33.8
14 Chaetomorpha 70.9 7.7 6.8 11.4 0.1 – – 32.5
15 Cladophora 71.6 8.0 7.1 10.6 0.9 – – 33.3
16 Oedogonium 72.1 8.1 6.3 10.4 1.3 – – 33.7
17 Cladophora FW 71.1 8.3 6.8 10.6 1.3 – – 33.5
18 Aspen wood 75.2 8.2 0.5 15.8 0.3 0.48 3.8 34.3 Pedersen et al. [13]
19 Scenedesmus 72.6 9.0 6.5 10.5 1.35 – – 35.5 Vardon et al. [14]
20 Defatted scene 72.2 8.9 7.8 10.5 0.90 – – 35.3
21 Spirulina 72.2 9.1 8.1 9.2 1.41 – – 35.8
22 Nutrient depleted Oedogonium 65.8 8.5 1.5 18.3 – – – He et al. [15]
23 Spent coffee grounds 71.2 7.1 3.0 18.7 – – – 31.00 Yang et al. [16]
24 Pinus 60.1 6.0 1.2 32.7 0.1 – – 23.1 Cao et al. [17]
25 Cupressus funebris 62.0 6.6 1.6 29.8 0.1 – – 25.1
26 Platanus 70.0 6.3 0.7 23.0 0.01 – – 28.6
27 Cinnamomum Camphora 74.0 8.4 1.5 16.1 0.01 – – 34.2
28 Pittosporum tobira 71.0 8.5 1.5 19.0 0.01 – – 32.9
29 Distylium racemosum 64.1 6.8 0.7 28.4 0.01 – – 26.3
30 Viburnum odoratissimum 71.7 8.1 1.2 19.0 0.01 – – 32.5
31 Salix alba 73.7 9.2 3.1 14.1 0.01 – – 35.6
32 Algal waste of Indiana polis 71.4 8.36 4.92 15.4 – – – 33.3 Chen et al. [18]
33 Swine manure 71 8.9 4.1 0.21 14.2 35 – – 61 Toor et al. [19]
34 Garbage 73.6 9.1 4.6 12.7 36 – – 21
35 Indonesian biomass residue 67–80 6–8 0–2 11–23 30 – – 21–36
36 Sawdust, rice husk, lignin – – – 8
37 Beech wood 76.7 7.1 0.1 16.1 34.9 – – 28
38 Phytomass 76.6 7.6 2.1 0.1 13.6 – – –
39 Algae Dunaliella tertiolecta 63.55 7.66 3.71 25.8 30.7 – – 25.8
40 Porphyridium 66–83 5–11 0–12 0–1 8–27 22.8–36.9 – – 5–25
41 Nannochloropsis 51 7 9 0.6 28.8 3 – 46 Valdez et al. [20]
42 Acid mine drainage 68.8 7.9 7.1 – – 29.70 Raikova et al. [21]
43 Cyanobacteria sp. 76.02 9.10 6.29 7.44 1.15 – – 36.51 Huang et al. [22]
44 Bacillariophyta sp. 76.09 9.11 5.60 8.28 0.92 – – 36.45
45 Seaweed 75.54 9.16 3.65 11.66 0.62 – – 35.97 Bach et al. [23]
46 L.digitata 70.5 7.8 4.0 17 0.7 – – 32 17.6 Anastasakis and Ross [24]
47 L.hyperbore 72.8 7.7 3.7 14.9 0.8 – – 33 9.8
48 L.saccharina 74.5 7.9 3.0 14.0 0.6 – – 33.9 13
49 A.esculenta 73.8 8 3.8 14 0.8 – – 33.8 17.8
50 L.Saccharina 31.3 3.7 2.4 26.3 0.7 24.2 9.2 12
51 Taihu cyanophyta 77.30 12.08 1.10 9.01 – – 41.73 Guo et al. [25]
52 Coffee Husk 43.13 5.02 1.55 32.78 0.67 7.4 8.44 16.79 Braz et al. [26]
53 Tucuma Seed 48.83 6.12 0.88 32.20 – 5.97 6.08 20.77
54 Sugarcane 45.05 5.57 0.25 37.91 – 3.21 6.95 20.77
55 Peanut shell 41.52 7.43 2.12 27.96 0.60 12.80 7.98 16.52
56 Rice husk 31.47 6.67 1.04 23.03 0.50 29.53 8.19 15.39
57 Pine sawdust 45.95 7.47 0.32 34.32 0.57 4.71 6.90 17.03
58 Pond water algae biomass 46.09 6.22 9.70 37.35 0.64 Nautiyal et al. [27]
59 Spirulina 48.10 6.97 10.14 34.13 0.66
60 Chlorella 51.33 7.90 9.80 30.38 0.59
61 Pond water algae oil 59.94 11.57 0.11 28.37 0.31
62 Spirulina oil 66.73 12.40 0.50 20.21 0.16
63 Cladophora glomerata 26.8 3.53 2.14 20.48 0.22 36.5 9.1 10.29 Plis et al. [28]
64 Posidonia Oceanica 35.5 3.60 0.27 28.85 0.18 26.1 5.5 12.82
65 Nannochloropsis gaditana 40.3 5.97 6.30 14.49 0.37 28.3 4.1 18.53
66 Microcystis 42.26 6.27 7.88 43.07 0.52 6.14 9.59 16.2 Hu et al. [29]
67 Almeriensis 41.78 6.81 7.94 42.93 0.55 14.5 17.6 Diaz-Rey et al. [30]
68 S.japonica 34.7 5.5 1 41.6 0.3 18.3 7.4 12.1 Choi et al. [31]
69 S.pallidum 22.64 4.90 2.96 21.34 1.42 36.44 10.30 9.63 Li et al. [32]
70 P.elongata 35.81 5.93 6.86 51.40 27.45 11.55 12.54 Ceylan et al. [33]
71 Sargassum sp 26.70 4.23 1.35 67.53 36.82 9.34 10.10
72 U.fasciata 25.64 5.75 3.13 5.52 16 19.86 Trivedi et al. [34]
(continued on next page)

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Table 1 (continued)

S.No Feedstock Elemental composition of product species after HTL References

C (%) H (%) N (%) O (%) S (%) Ash (%) Moisture (%) HHV % Yield

73 Xuzhou SS 47.4 7.9 8.2 35.2 1.3 56.8 5.6 Huang et al. [35]
74 S.patens C.Agardh 17.7 14.38 15.47 Li et al. [36]
75 E.grandis 47.19 5.77 0.21 46.59 0.24 0.09 18.07 Louw et al. [37]
76 T.suesica 43.32 7.27 5.75 40.55 3.11 12.20 7.88 Zainan et al. [38]
77 Dunaliella tertiolecta 53.3 5.2 9.8 31.7 – 19.8 Minowa et al. [39]
78 Chlorella vulgaris 52.6 7.1 8.2 32.2 0.5 23.2 Biller and Ross [40]
79 Nannochloropsis oculata 57.8 8.0 8.6 25.7 – 17.9
80 Botryococcus braunii 77.04 12.40 1.23 9.86 0.18 35.6 Liu et al. [41]
81 Fucus vesiculosus 32.88 4.77 2.53 35.63 2.44 11.8 15.0 Ross et al. [42]
82 Chorda filum 39.14 4.69 1.42 37.23 1.62 9.9 15.55
83 Laminaria digitata 31.59 4.85 0.90 34.16 2.44 10 17.60
84 Fucus Serratus 33.5 4.78 2.39 34.44 1.31 18.6 16.66
85 Laminaria hyperborea 34.97 5.31 1.12 35.09 2.06 11.2 16.54
86 Macrocystis pyrifera 27.3 4.08 2.03 34.8 1.89 18.5 16.0
87 Miscanthus 46.32 5.58 0.56 41.79 0.2 2.1 19.08
88 Nannochloropsis Salina 55.16 6.87 2.73 33.97 1.27 2.48 4.95 25.40 Toor et al. [43]
89 Mougeotia 41.51 5.59 5.40 27.03 0.51 19.96 5.14 16.63 Sharara et al. [44]
90 Cladophora 33.79 4.73 6.35 21.27 1.57 32.29 5.09 14.53
91 Seaweed meal 43.99 5.95 5.21 36.13 1.02 7.7 7.92 18.35 Lorenzo et al. [45]
92 Synechococcus/Anabaena 42.78 7.74 7.91 38.1 7.4 9.61 Wagner et al. [46]
93 Synechocystis 46.12 7.98 3.52 11.2 4.5 15.37
94 A.azuera 40.82 5.56 0.63 52.99 10.61 6.03 52.99 Aysu et al. [47]
95 Chlorella.sp 47.54 7.1 6.73 38.63 5.93 6.8 18.59 Phukan et al. [48]
96 E.prolifera 35.20 5.20 2.10 32.98 15.91 8.61 13.4 Yang et al. [49]
97 Datura Stramonium L 43.55 5.98 0.77 49.70 6.38 3.73 14.39 Aysu and Durak [50]
98 E.Spectabilis 39.27 6.54 1.28 52.91 4.6 5.6 13.17 Aysu et al. [51]
99 Brewers spent grain 46.6 6.85 3.54 42.26 0.74 4.5 8 20.39 Mahmood et al. [52]
100 Laurel algae 48.97 6.38 3.02 41.63 10.53 9.95 19.77 Ertas and Alma [53]

1.2.1.1 Cellulose 1.2.2 Wet biomass feedstock

The chemical formula of the cellulose is denoted by (C6H10O5)n
which is a long chain polysaccharide, high molecular weight, and with
high degree of polymerization. Cellulose is a non-polar compound at
ambient temperature, but tends to soluble with the increase in the
temperature [54]. Monomers of glucose are stiffly bonded possessing
the formation of strong intramolecular and intermolecular interactions
amongst hydrogen bonds that originates the glucose monomers [55].
1.2.1.2 Hemicellulose
It is a branched structure hetero polymer with amorphous structure
embracing pentose and hexose as a polymer. The composition of the
hemicelluloses varies significantly for woody biomass and the grassy
biomass which comprises xylan in the earlier and mannan, glucan and
galactan in the later [56]. Further, hemicellulose in comparison to the
cellulose possess the weaker structure and less resistant to intramole-
cular hydrogen bonding allows the easier disintegration of the mole-
cules [57]. Hence, the conducive nature to hydrolysis of hemicellulose
is severe and prone to easy miscibility characteristic [58].
1.2.1.3 Lignin
The other fraction of the lignocellulose biomass is lignin which is
treated as a natural polymer can be referred as an aromatic compound
in which phenyl-propane with hydroxyl and ethoxy groups are linked
via ether bonds [59]. Lignin possess similar morphological character-
istic of amorphous form as hemicellulose, less solubility similar to
cellulose and the peculiar behaviour of hydrophobic nature. Also it
possesses the binding capacity of stem cells or fibrous contents of
plants fibrous contents of the plant to strengthen cell wall structure,
improves the sublimation capacity of micro-organisms and to store the
energy [60]. In contrast to other bioorganic compounds the decay rate
of lignin is very low, in other words, it is resistant to biological
degradation. The significant feature of lignin encompasses the higher
energy content compared to the other two compounds that leads to
higher heating value to the product and considered to be the most
valuable phenol compound [61].
1.2.2.1 Lipids/Fats
These are majorly non-polar compounds otherwise immiscible/
hydrophobic in nature that resembles the similarities with the aliphatic
compounds and particularly referred to triglycerides (TAG's) nothing
other than triesters of fatty acids and glycerol [62]. At normal
temperatures, the fats are generally insoluble in solvents and gradually
tends to be polar with the change in temperature. The similar
phenomenon on the effect of the temperature on the solubility of the
fats can be seen in the case of cellulose. The dielectric constant of the
solvent in particular water at sub-critical conditions allows the greater
miscibility [57]. This leads to the stability in the structure of the TGA's
further leading to the formation of the glycerol a major by-product of
the bio-diesel production which is a combination of fatty acids,
methanol and salts. During HTL, glycerol is not converted to any oily
phase rather it turns to be a water-soluble compound [63]. Further
degradation of glycerol leads to the product stream of acetaldehydes,
propionaldehyde, acrolein, allyl alcohol, ethanol, formaldehyde, CO,
CO2, and H2 [62].
1.2.2.2 Proteins/Amino acids
One of the major constituent of microbial or algal biomass is
protein consisting several chains of peptide reduces to polymers of
amino acids. They are the building blocks of proteins and highly
heterogeneous and hence the complexity in degrading the amino acids
is challenging. The strong peptide chain of proteins undergoes dec-
arboxylation, and deamination reaction upon hydrothermal liquefac-
tion leads to the formation of hydrocarbons, amines, aldehydes and
acids [19]. Further degradation resulting carboxylic acids, acetic acid,
propionic acid, n-butyric acid, and iso-butyric acids.
2. Evolution of HTL process over decades
Environmental issues, sustainability, declining fossil fuels, and
energy security concerns have led the world to explore alternate, clean,

4
A.R.K. Gollakota et al.
cheap and renewable energy sources. Though biomass is one of the
prominent option for renewable and sustainable energy, choosing the
reliable and efficient conversion methodology is a big challenge. Over
the decades of research lightened different thermo-chemical conversion
technologies and each of them has their own advantages and dis-
advantages. In this regard, HTL is found to be the suitable process
available to tackle the wet feed stock conversion to fuel energy.
Research on HTL can date back to the 1930s and there is considerable
amount of literature available worldwide pertaining the wet biomass
conversion. The pioneering work on the HTL process on a commercial
scale of cellulose biomass to heavy oil was initiated at Pittsburgh
Energy Research Centre in 1970. This process of HTL was taken
further by Schaleger et al. [64] at Lawrence Berkeley Laboratory,
Thigpen [65] at Albany Biomass Liquefaction Experimental Facility.
Further details of studies of the HTL process by several researchers are
briefly described below.
Beckman and Elliott [66] performed comparison studies on yields
and properties of oil obtained from direct thermochemical biomass
liquefaction process. The authors developed correlations for the key
parameters such as temperature, pressure, time, catalyst and con-
cluded that the changes in the governing parameters has a significant
impact on the product output. White and Wolf [67] developed a unique
method of pumping concentrated viscous biomass slurries through
liquefaction system. The authors introduced the extruder – feeder
system to pump the high viscous liquids for the liquefaction process.
One of the pioneering works of the HTL of microalgae with high lipid
content was done by Dote et al. [68]. In the years that followed several
researchers had begun to explore this technology and verified the
properties of algae bio-oil in comparison with the petroleum Minowa
et al. [39]. Itoh et al. [69] developed a scale up of HTL of sewage sludge
operating at temperature of 300 °C and pressure of 10 MPa. Sawayama
et al. [70] studied energy consumption for the HTL process of various
algae and presented the energy consumption ratio for the HTL could
produce net energy with low energy consumption. Also HTL opens up
new possibilities for combined fuel production and waste water
treatment in densely populated areas where large amounts of wet
waste materials are available. Behrendt et al. [71] reviewed the direct
liquefaction especially for lignocellulose biomass through sub critical
and super critical solvents. Since 2009, the study gradually grabbed the
attention of some reputed international research laboratories exploring
the liquefaction reaction parameters that includes residence time,
reaction temperature, catalyst selection and loading. Peterson et al.
[57] provided a comprehensive overview on the hydrothermal liquefac-
tion of bio-oil from biomass using sub and super critical water or
solvent extraction technique. Further the products of HTL process
comprises a wide range of value added chemical compounds which
include branched aliphatic compounds, aromatics and phenolic deri-
vatives, carboxylic acids, esters, and nitrogenous ring structures Xiu
et al. [72]. Savage [73] published a brief but insightful overview on the
hydrothermal liquefaction of microalgae. This was supported by the
several other researches of Alba et al. [74], Minowa et al. [39], Ross
et al. [75], Vardon et al. [14], Zou et al. [76]. Researchers have recently
posted a renewable algal biorefinery based on HTL of algae Jena et al.
[77], Alba et al. [74,78]. Recently the prominence of algae as the
feedstock for HTL is addressed by Barreiro et al. [10] and Chow et al.
[79]. Latest review of Elliott et al. [80] and Jindal and Jha [81]
enlightened some of the previous and current research works on
hydrothermal liquefaction of biomass (both solid and liquid) which
included studies of Appell et al. [82], Kaufman et al. [83], Inoue et al.
[84], Chornet and Overend [85], Ocfemia et al. [86], Heilmann et al.
[87], Elliott [7], Akhtar and Amin [88], Xu et al. [89] and Tekin et al.
[90].
Further literature pertaining to the reaction mechanisms of HTL is
critical in understanding the process so as to better design the reactors
and control the process. At present, understanding of HTL mechanisms
is largely qualitative and indicative although efforts have been made
5
Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
through years by many researchers Balat [91], Demirbas [92,93],
Minowa et al. [94], Yuan et al. [95]. Generally, biomass is first broken
up into fragments by hydrolysis, and then degraded into smaller
compounds by dehydration, dehydrogenation, deoxygenation and
decarboxylation. At the end, some complex chemicals may be synthe-
sized by repolymerization. Biocrude product generated in the repoly-
merization process usually contains acids, alcohols, aldehydes, esters,
ketones, phenols and other aromatic compounds Chornet and Overend
[85]. Hietala et al. [95] introduced new dimensions of kinetic model for
fast hydrothermal liquefaction of biomass with good yield of 41% at
400 0C and short residence time. However, the exact mechanisms or
pathways of the HTL still remain unclear mainly due to the complexity
of the feedstock and HTL products, as well as the seemingly-infinite
possible intermediate reactions. Hydrothermal liquefaction now is in
the transient state from lab-pilot scale to pilot-industrial scale, which
makes the mechanisms study more important and urgent. With the
support of mechanisms work, development of large-scale units could be
more reasonable and high-grade products may be produced, adding a
solution to current environmental and energy problems.
Recently, immense amount of the work pertaining to hydrothermal
liquefaction of wet and dry biomass through different techniques has
been carried out by many researchers. For instance, Alhassan et al. [96]
presented glimpses of HTL process on dry biomass and obtained bio-
oil with properties equivalent to pyrolysis oil. Costanzo et al. [97]
obtained bio-oil derived from wet biomass and reported that the
composition of the bio-oil is equivalent to conventional gasoline.
Further, to obtain higher percentages of yield Lavanya et al. [9]
introduced the blending of algal crude to petro crude that is turned
to diesel fraction. Pedersen et al. [13] obtained aspen wood derived
bio-oil characteristics equivalent to gasoline which supports the
research work of Costanzo et al. [97]. Zhu et al. [98] reported that
hydrothermal liquefaction of wet and dry biomass results in the higher
yields of phenolics at the conventional operating temperatures rather
than desired aromatics. Maddi et al. [99] made an attempt to obtain
value added chemicals through hydrothermal liquefaction of bio-oil
and succeeded in obtaining the same. Another important aspect of this
HTL process is the introduction of continuous flow reactor which yields
a significant amount of heating values which was reported by Pedersen
et al. [13]. Recent review of Elliot et al. [80] also stressed the
importance of introducing the continuous flow reactors rather than
conventional batch process for the higher yields of HTL products.
Several other explorations on the critical parameters such as energy
consumption economics by Sawayama et al. [70]; reaction mechan-
isms/pathways [91–94,100]; algal biomass as feedstock [97,74,78];
generation of value added chemicals by Xiu et al. [72]; temperature,
pressure, reaction residence time and catalyst loading effects by
Anastasakis and Ross [101] and more insights by several researchers
[36,40,75,76,82,84–89,102–104] are praiseworthy. Finally, Table 2
presents the comprehensive details of aforementioned and some more
literature in tabular form pertained to various aspects of hydrothermal
liquefaction over the years.
In the past decade, there were also several review papers on various
aspects of HTL. For instance, Peterson et al. [57] presented sub- and
supercritical water technologies available for thermochemical biofuel
production from various types of biomass. Toor et al. [134] reviewed
the subcritical water technologies for production of biocrude from
biomass; and they summarized that the chemical properties of bio-
crude are highly dependent of the biomass composition. Akhtar and
Amin [88] reviewed the literature pertaining to HTL of biomass with
the aim to report process conditions such as final liquefaction
temperature, residence times, rate of biomass heating, size of biomass
particles, types of solvents, etc. for optimum bio-oil yield. They have
also included brief discussion on decomposition mechanisms during
hydrothermal liquefaction. Tekin et al. [90] explained the physico-
chemical properties of water under subcritical and supercritical condi-
tions on HTL and interactions of water with biomass during HTL
 Table 2
Summary of literature pertained to hydrothermal liquefaction of biomass (both wet and dry).

S. No Author Description Feed Process conditions Products

1 Alhassan et al. [96] Hydrothermal liquefaction of de-oiled Jatropha curcas cake using deep De-oiled Jatropha curcas cake Temp: 250 °C HHV values of the HTL bio oil is 25.01 MJ/kg.
eutectic solvents (DESs) as catalyst and co solvents Pressure: 4.5 MPa
A.R.K. Gollakota et al.

2 Anastasakis and Ross
[24]
3 Bach et al. [23]
4 Barriero et al. [10]
5 Caporgno et al. [11]
6 Chan et al. [105]
7 Chen et al. [18]
Reactor: Batch
Hydrothermal liquefaction of four brown macro algae commonly found Digitata, hyperborea, saccharina, Temp: 350 °C High nitrogen content is observed from the bio oil obtained
on the UK coasts: An energetic analysis of the process and comparison esculenta Pressure: indicating the necessity for upgradation.
with bio-chemical conversion methods Reactor: Batch
Fast hydrothermal liquefaction of Norwegian alga-Screening tests Laminaria saccharina Temp: 350 °C Highest yield of 79% bio-oil is obtained with 35.97 MJ/kg HHV.
Pressure: 16.5 bar
Reactor: Muffle
furnace
Hydrothermal liquefaction of microalgae: Effect on the product yields of Nannochloropsis gaditana, Temp: 350 °C Organic solvent dichloromethane increases the yield of biocrude at
the addition of an organic solvent to separate the aqueous phase and the Scenedesmus almeriensis Pressure: 2 MPa higher oxygen and nitrogen contents.
biocrude oil Reactor: Micro
autoclave
Hydrothermal liquefaction of Nannochloropsis Oceanica in different Nannochloropsis Oceanica Temp: 240–300 °C Alcohol co solvents yield high bio oil ~60%.
solvents Pressure: 32–
43 bar
Reactor: Batch
Effect of process parameters on hydrothermal liquefaction of oil palm Raw fruit bunch, palm Mesocarp Temp: 330–390 °C Optimum bio oil yield is obtained at 390 °C and 25 MPa
biomass for bio-oil production and its life cycle assessment fibre and palm kernel shell Pressure: 25–
35 MPa
Reactor: Batch
Hydrothermal liquefaction of mixed culture algal biomass from waste Feedstock from One water INC. Temp: 260–320 °C HHV values of 33.3 MJ/Kg is viable with hydrocarbons, fatty acids,
water treatment system into bio-crude oil Indianapolis Pressure: 1 MPa cyclic amines.
Reactor: Batch

6
8 Costanzo et al. [97] Effect of low temperature hydrothermal liquefaction on catalytic Sorokiniana, minutissima, bijuga Temp: 225 °C Bio oil with similar composition to gas oil obtained via HTL/HDO
hydrodenitrogenation of algae bio crude and model macromolecules Pressure: 20.7 bar process using Ru/C catalyst.
Reactor: Batch
9 David et al. [106] Review and experimental study on pyrolysis and hydrothermal Nannochloropsis Temp: 250 °C Algal HTL is very handy when compared to pyrolysis in terms of
liquefaction of microalgae for biofuel production. Pressure: 10– yield.
25 MPa
Reactor:
Continuous
10 Eboibi et al. [107] Hydrothermal liquefaction of microalgae for biocrude production: Tetraselmis, Spirulina Temp: 300–350 °C The highest HHV of 40 MJ/kg was obtained after the process for
improving the biocrude properties with vacuum distillation Pressure: 30 bar the specified feedstock.
Reactor: Batch
11 Guo et al. [25] A review of bio-oil production from hydrothermal liquefaction of algae Algal feedstock Temp: 430–530 °C Free fatty acids, phenols and aromatic compounds.
Pressure: 24–
34 MPa
Reactor: Batch
12 Guo et al. [108] Hydrothermal liquefaction of cyanophyta: Evolution of potential bio- Cyanophyta Temp: 370 °C High temperatures favoured phenols, benzenes, alkanes and fatty
crude oil production and component analysis Pressure: 1.5Psi acids and low temperatures favoured alkanes and heterocyclic
Reactor: Batch compounds.
13 Haarlemmer et al. Analysis and comparison of bio oils obtained from hydrothermal Beech wood Temp: 300 °C High iodine value bio oil is obtained
[109] liquefaction and fast pyrolysis of beach wood Pressure: 1 MPa
Reactor: Batch
14 Hadhoum et al. [110] Hydrothermal liquefaction of mill waste water for bio-oil production in Oil mill waste water Temp: 200–300 °C A maximum yield of 58 wt% was achieved having majority content
subcritical conditions Pressure: 190 bar of phenolics.
Reactor: Batch
15 He et al. [15] Continuous hydrothermal liquefaction of macro algae in the presence of Oedogonium Temp: 300–350 °C Presence of co solvent has minor effect on the product yield.
organic co-solvents Pressure: 10 bar
Reactor: Batch
16 Hietala et al. [95] A quantitative kinetic model for the fast and isothermal hydrothermal Nannochlorosis Sp Temp: 100–400 °C Bio crude yield as high as 46% is achievable at 400 °C and 1 min
liquefaction of Nannochlorosis Sp Pressure: 400 bar residence time.
(continued on next page)
Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
 Table 2 (continued)

S. No Author Description Feed Process conditions Products

Reactor: Batch
17 Hognon et al. [111] Comparison of pyrolysis and hydrothermal liquefaction of c. reinhardtii Temp: 220–310 °C Yield of bio-oil is higher in pyrolysis and energy ratios are higher in
Chlamydomonas reinhardtii. Growth studies on the recovered Pressure: 10 MPa HTL.
A.R.K. Gollakota et al.

hydrothermal aqueous phases Reactor: Batch

18 Gao et al. [17] Bio-oil production from eight selected green landscaping wastes through Landscape waste leaves Temp: 300 °C The presence of value-added chemicals, phenolics, ketones, esters,
hydrothermal liquefaction Pressure: 2 MPa acids, and alcohols, in bio-oils are confirmed
Reactor: Batch

19 Lavanya et al. [9] Hydrothermal liquefaction of freshwater and marine algal biomass. Arthrospira Platensis, tetraselmis Temp: 200–350 °C Introduced a procedure to blend algal crude to petrocrude and
sp Pressure: 180 bar yielding 18% diesel fraction.
Reactor: Batch

20 Lyu et al. [112] Two stage nanofiltration process for high-value chemical production Rice straw Temp: 300 °C TNSF hydrolysates into three parts: sugar concentrates, mono
from hydrolysates of lignocellulose biomass through hydrothermal Pressure: 12 MPa phenols, cyclopentanones, acid acids.
liquefaction Reactor: Batch
21 Maddi et al. [99] Quantitative characterization of the aqueous fraction from hydrothermal Chlorella, Scenedesmus obliques, Temp: 350 °C Acetic acid, propanic acid, pyridine, acetone, ethanol and other
liquefaction of algae Tetraselmis Pressure: 20.7 MPa organic chemical compounds are quantified.
Reactor:
Continuous
22 Meryemoglu et al. Biofuel production by liquefaction of Kenaf biomass Kenaf and wheat straw biomass Temp: 200–350 °C Higher yields are seen at 300 °C and reduced thereafter.
[113] Pressure: 5 MPa
Reactor: Batch
23 Nazari et al. [114] Hydrothermal liquefaction of woody biomass in hot compressed water: Birch wood saw dust Temp: 300 °C Occurence of phenolic derivatives and aliphatic compounds
catalyst screening and comprehensive characterization of bio-crude oils Pressure: 90 bar increased significantly in the presence of catalyst than without
Reactor: Stirred catalyst.

7
reactor
24 Neveux et al. [12] Bio crude yield and productivity from the hydrothermal liquefaction of Oedogonium, Derbesia, Ulva Temp: 350 °C Derbesia > Ulva > Oedogonium. This is the sequence of the
marine and fresh water green microalgae Pressure: 250 bar higher biocrude produced
Reactor: Batch
25 Patil et al. [115] Hydrothermal liquefaction of wheat straw in hot compressed water and Wheat straw Temp: 350 °C A maximum of 28 MJ/kg HHV is obtained.
subcritical water-alcohol mixtures Pressure: 200 bar
Reactor: Tubular
26 Pedersen and Production of fuel range oxygenates by supercritical hydrothermal Aspen wood Temp: 400 °C The majority groups obtained are cyclopentanones and oxygenated
Rosendahl [116] liquefaction of lignocellulosic systems Pressure: 300 bar aromatics.
Reactor: Batch
micro
27 Pedersen et al. [13] Continuous hydrothermal co-liquefaction of aspen wood and glycerol Aspen wood and glycerol mixture Temp: 400 °C Bio crude with high quality of 34.3 MJ/kg HHV value, and valuable
with water phase recirculation Pressure: 300 bar chemicals in the range of C6-C12 similar to gasoline.
Reactor:
Continuous
28 Raikova et al. [21] Assessing hydrothermal liquefaction for the production of bio-oil and Arthrospira platensis, Temp: 310–350 °C HTL produced bio-oil for upgrading process from the acid mine
enhanced metal recovery from microalgae cultivated on acid mine Chlamydomonas sp Pressure: 120 bar drainage also the prevention of AMD.
drainage Reactor: Batch
29 Reddy et al. [117] Temperature effect on hydrothermal liquefaction of Nannochloropsis Nannochloropsis gaditana and Temp: 300 °C Higher yields of HHV of 39MJ/kg is possible with the feedstock.
gaditana and Chlorella sp Chlorella sp Pressure: 200Psi
Reactor: Batch
30 Shakya et al. [118] Effect of temperature and Na2CO3 catalyst on hydrothermal liquefaction Nannochloropsis, Pavlova, Temp: 250–350 °C Bio oil with heating value of 37 MJ/kg is obtained which is
of algae Isochrysis Pressure: 35Psi equivalent to heavy crude oil.
Reactor: Batch
31 Singh et al. [119] Catalytic hydrothermal liquefaction of water hyacinth Water hyacinth Temp: 250–300 °C Maximum bio-oil yield of 23% is obtained using catalyst KOH and
Pressure: 1300Psi K2CO3 with less oxygen.
Reactor: Batch
32 Singh et al. [120] Hydrothermal liquefaction of rice straw: Effect of reaction environment Rice straw Temp: 280–320 °C Bio oil yield of 17% and 78% conversion with ether soluble bio-oil
Pressure: 6–9 MPa under O2 environment.
(continued on next page)
Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
 Table 2 (continued)

S. No Author Description Feed Process conditions Products

Reactor: Autoclave
33 Sudasinghe et al. Hydrothermal liquefaction oil and hydrotreated product from pine Pine Temp: 400 °C Fusion of FT-ICR further simplified in identification of the
[121] feedstock characterized by hetero nuclear two dimensional NMR Pressure: 3000 Psi compounds present in the bio-oil obtain through HTL process.
A.R.K. Gollakota et al.

spectroscopy and FT-ICR mass spectrometry Reactor:

Continuous
34 Tekin et al. [122] Hydrothermal liquefaction of beach wood using a natural calcium borate Beach wood Temp: 250–350 °C Most of the product stream is of phenols, with an optimum HHV of
mineral Pressure: 4– 23.81MJ/kg
16.5 MPa
Reactor: Batch
35 Tian et al. [123] Hydrothermal liquefaction of harvested high –ash low lipid algal biomass Algal blooms of Dianchi lake Temp: 260–340 °C 18.4% yield of biocrude with highest content of ash 41.6% is
from Dianchi lake: Effects of operational parameters and relations of Pressure: 3 MPa obtained through the feedstock.
products Reactor: Batch
36 Tran [124] Fast hydrothermal liquefaction for production of chemicals and biofuels Wet slurry feed Temp: 374 °C Possible challenges and current status of possible solutions to the
from wet biomass using a plug flow reactor Pressure: 22.1 MPa challenges, focusing on the need of developing a special plug-flow
Reactor: Plug flow reactor for scaling up of the HTL process
reactor
37 Valdez et al. [20] Hydrothermal liquefaction of nannochlorpsis sp: Systematic study of Nannochlorpsis sp: Temp: 250–400 °C
process variables and analysis of the product fractions Pressure: 30000Psi
Reactor: Batch
38 Vardon et al. [14] Thermochemical conversion of raw and defatted algal biomass via Scenedesmus, Spirulina Temp: 300–450 °C Wet algal biomass favours the HTL process that yields higher HHV
hydrothermal liquefaction and slow pyrolysis Pressure: 10– values of 35–37 MJ/kg
12 MPa
Reactor: batch
39 Wang et al. [125] Hydrothermal liquefaction of Litsea Cubeba seed to produce bio-oil Litsea Cubeba Temp: 290 °C The liquefied bio-oil was characterized in higher C,H, content and
Pressure: – much lower N content.
Reactor: Batch

8
40 Wang et al. [126] Hydrothermal liquefaction of lignite, wheat straw and plastic waste in Lignite, wheat straw Temp: 260–320 °C Adding tourmaline during HTL increases the oil yield, higher
sub critical water for oil: product distribution Pressure: 2–5 MPa conversion rates.
Reactor: Batch
41 Xu and Etcheverry Hydro liquefaction of woody biomass in sub and super critical ethanol Jack pine wood Temp: 473–623 K High yield bio-oil of 63% with FeSO4 catalyst with dominant
[127] with iron based catalysts Pressure: 2– phenolic compounds.
10 MPa
Reactor: Batch
42 Xu et al. [89] Hydrothermal liquefaction of Chlorella pyrenoidosa for bio-oil Chlorella pyrenoidosa Temp: 300 °C Zeolite Ce/HZSM-5 exhibits good potential for preparation of bio-
production over Ce/HZSM-5 Pressure: oil from microalgae with high efficiency
Reactor: Autoclave
43 Yan et al. [128] Composition of the bio-oil from the hydrothermal liquefaction of duck Duckweed Temp: 350 °C Extraction solvents with high polarity yields higher % of bio oil of
weed and the influence of the extraction solvents Pressure: 5 kPa 26%.
Reactor: Batch
44 Yang et al. [16] Hydrothermal liquefaction of spent coffee grounds in water medium for Spent coffee ground Temp: 200–300 °C A maximum of 31 MJ/kg HHV value of bio oil is formed
bio-oil production Pressure: 0.5–
2 MPa
Reactor: Autoclave
45 Yim et al. [129] Metal oxide catalysed hydrothermal liquefaction of Malaysian oil palm Malaysian oil palm Temp: 390 °C The presence of phenols, ketones, aromatic carboxylic acids are
biomass to bio-oil under super critical conditions. Pressure: 25 MPa confirmed.
Reactor: Batch
46 Zhang et al. [130] Hydrothermal liquefaction of Chlorella pyrenoidosa in Ethanol-water for Chlorella pyrenoidosa Temp: 280 °C Ethanol water solution has best yield of 57.3 wt% biocrude.
bio crude production Pressure: 1 MPa
Reactor: Batch
47 Zhang et al. [131] Thermo gravimetric and kinetic analysis of bio crude from hydrothermal Enteromorpha prolifera Temp: 573 K A two step mechanism will be a better perspective in optimizing the
liquefaction of Enteromorpha prolifera Pressure: 1 MPa kinetics of HTL process.
Reactor: Batch
48 Zheng et al. [132] Alkaline hydrothermal liquefaction of swine carcasses to bio-oil Swine carcasses Temp: 250 °C 62.2 wt% of bio-oil and 22 wt% solid residue is obtained
Pressure: –
Reactor: Batch
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Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

The crude bio-oil composition is adjusted by reducing the amount

process. Tian et al. [156] presented review on HTL from algal

More phenolic, less carboxylic compounds with catalytic activity

prospective for algal biorefinery including the factors such as feedstock

and high carbon and energy recovery without any catalyst is

preparation, scale-up of algae HTL and process integration. Guo et al.
[25] also presented the details of research works pertaining to
production of bio-oil from HTL of algae and reported that the proper-
ties of resulting bio-oil from HTL are affected by temperature, reaction
time, algae species, algae concentration, reaction atmosphere, catalysts
and sub and supercritical water reaction conditions. Elliott et al. [80]
presented the review of research papers of HTL with aim to describe
evolution of HTL processes from batch to continuous state. Further
they described the mass and energy balances from the existing process
models which are used for process costs calculations with the aim to
provide optimum way for commercial likelihood of technology. Jindal
of phenols and acids

and Jha [81] reviewed effects of process variables such as biomass

composition, temperature, residence time, pressure, biomass heating
rate, particle size, catalysts, etc. on the yield and quality of bio oil.
Products

observed.

Dimitriadis and Bezergianni [147] presented review on HTL of various

feedstock such as woody biomass, wastes, plastics and microalgae for
bio-crude production through HTL. On the other hand, this article
Process conditions

briefly reviewed the elemental composition of bio-crude obtained by

Temp: 280–400 °C

Reactor: Autoclave
Pressure: 350 bar

HTL, different types of feedstock adopted for HTL, mechanism of HTL

Reactor: Batch

processes, possible process flow diagrams for HTL of both wet and dry
Pressure: 90–
Temp: 300 °C

biomass and energy efficiency of the process. In addition, this article

112 bar

also enlisted a possible future research scope for concerned research-

ers.

3. HTL process mechanism

The mechanism of the hydrothermal liquefaction has not been

elucidated much in the literature. The pathway of HTL comprises three
major steps, depolymerisation followed by decomposition and recom-
bination [19]. The details of these are explained in the further sections.
Barley straw

Barley straw

Briefly, biomass is decomposed and depolymerized in to small com-

pounds. These compounds may be highly reactive, thus polymerizing
Feed

and forming bio crude, gas and solid compounds is essential. Further
the critical process parameters such as temperature, residence time,
the process of repolymerization, condensation and decomposition of
Hydrothermal liquefaction of barley straw to bio-crude oil. Effects of

the components from the different phases may vary accordingly. Since
biomass is a complex mixture of carbohydrates, lignin, proteins, and
Influence of alkali catalyst on product yield and properties via

lipids, the reaction chemistry and mechanisms of biomass liquefaction

are consequently also complex [135,136]. Fig. 1 presents the schematic
reaction temperature and aqueous phase recirculation's

overview of the reaction pathway and the details of the steps are
enlisted [137].

3.1. Depolymerisation of the biomass

hydrothermal liquefaction of barley straw

Depolymerisation of biomass is a sequential dissolving of macro-

molecules through utilization of their physical and chemical properties.
The intrinsic hemicellulose and cellulose biopolymers contributes
positively towards the thermal stability of the biofuel [138].
Depolymerisation process overcomes the difficulties and obstinate
properties of lignocellulose biomass that mimics the natural geological
Description

processes of producing fossil fuels. The decisive parameters tempera-

ture and pressure changes the structure of the long chain polymers
consisting of hydrogen, oxygen, and carbon to shorter chain hydro-
carbons [139]. Further, the energy contents of the organic materials are
recycled in the presence of water.
Zhu et al. [133]

3.2. Decomposition of the biomass monomers by cleavage,

Zhu et al. [98]

dehydration, decarboxylation and deamination

Table 2 (continued)

Author

This step involves the loss of water molecule (dehydration), loss of

CO2 molecule (decarboxylation) and removal of amino acid content
(deamination) [140]. The dehydration and decarboxylation facilitate
S. No

the removal of oxygen from the biomass in the form of H2O and CO2
49

50

respectively. Biomass comprising macromolecules are hydrolysed to

9
A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Fig. 1. Reaction pathway of the hydrothermal liquefaction.

Biochar/fertilizer
Water
Recirculation

Biomass/ Hydrothermal Phase

Pre-treatment Hydrotreating Hydrocarbon Fuels
Wet Waste Liquefaction Separation

Aqueous Phase
Process Heat and
Aqueous Fertilizer
Anaerobic Digestion/ Power Integration
Hydrothermal gasification
H2

Fig. 2. Process flow diagram of HTL process of lignocellulose biomass adopted from Biller and Ross [148].

CO2

Water & Algae Hydrothermal

Water Removal Hydrotreating Hydrocarbon Fuels
Nutrients Cultivation Liquefaction

Solids, P recycle
Process Heat
Aqueous Phase and Power
Nutrients & CO2 Integration
Catalytic Hydrothermal
Gasification
H2

Fig. 3. Process flow diagram of HTL process of algal biomass/wet biomass adopted from Biller and Ross [148].

form polar oligomers and monomers [141]. Water at high tempera-
tures and pressure breaks down the hydrogen bonded structure of
cellulose and causes the formation of glucose monomers. Because
fructose is more reactive than glucose, it rapidly degrades in plethora of
products by the different types of reactions, including isomerization,
hydrolysis, dehydration, reverse-aldol defragmentation, rearrangement
and recombination reactions [142]. The majority of the degradation
products such as polar organic molecules, furfurals, glycoaldehydes,
phenols and organic acids are highly soluble in water.
3.3. Recombination and repolymerization of reactive fragments
This is the third step in which the reverse to the initial processing
steps are happening due to the unavailability of the hydrogen com-
pound [19]. If hydrogen is freely available in the organic matrix for the
liquefaction process the free radicals will be capped yielding the stable
molecular weight species. At conditions the unavailability of the
hydrogen or the concentration of the free radicals are excessively large,
the fragments are recombined or repolymerized to form high molecular
weight char compounds otherwise noted as coke formation [143].
3.4. Hydrothermal liquefaction process
Hydrothermal liquefaction is a biomass to bio-liquid conversion
route carried out in water at moderate temperature of 280–370 °C and
high pressures (10–25 MPa) that has a liquid bio crude as main
product along with the gaseous, aqueous and solid phase byproducts
[144]. The product stream of this process have high energy content and
unique feature of enhanced heat recovery in comparison to other
processes [145]. Many complex reactions take place during the
transformation of biomass into crude oil like products [146]. In this
regard, the process mechanism is classified for two types of feedstock
namely lignocellulose biomass (dry feedstock) and algal biomass (wet
feedstock). The sub classification or the major fractions of the dry/
lignocellulose biomass is hemicellulose, cellulose and lignin [147]. On
the other hand, the wet feed stock composition comprises of lipids,
proteins, carbohydrates and algaenans. The description of HTL of the
dry and wet feedstock of biomass are presented herein.
3.4.1. HTL of lignocellulose biomass
The reactor design in the hydrothermal processing can be either
batch or continuous. Continuous reactors require feeding system that
operate under pressure and include either slurry based pump or lock
and hopper systems for large particles. The detailed pathway of the
biomass to bio-crude through hydrothermal liquefaction of lignocellu-
lose biomass was shown in Fig. 2 adopted from Biller and Ross [148].
The feedstock requires pre-treatment especially the woody biomass for
the reasons of reducing the particle size, removing the contaminants,
and alkaline treatment to obtain a stable slurry for easy pumping. The
feedstock is then processed via HTL at temperature of around 350 °C

10
A.R.K. Gollakota et al.
Fig. 4. Schematic of Energy efficient usage HTL process using algal biomass. This figure was drawn from Refs. [150–156].
Table 3
Comparison of bio-crude by HTL and pyrolysis adopted from Elliot et al. [157].
Elemental composition Hydrothermal liquefaction
C (wt%) 73
H (wt%) 8 6
O (wt%) 16
S (ppm) < 45
Moisture 5.1
HHV (MJ/kg) 35.7
Viscosity (cPs) 15,000
and a pressure of 150 bar for 15 min approximately. Phase separation
occurs spontaneously at these operating conditions resulting the
gaseous stream of CO2, solid residue, bio-crude and small traces of
aqueous phase [149]. The aqueous phase/water can be recirculated to
HTL unit which reduces the water requirement and enhance the bio oil
yield. The other stream of the water that is generated through HTL
process can be treated anaerobically or via catalytic hydrothermal
gasification technique to produce methane rich or hydrogen rich
syngas. Anaerobic digestion of the water from the HTL process can’t
be treated to full extent due to the presence of phenols and furfurals
that delimits the anaerobic digestion process.
During the phase separation process the obtained solid phase
material can be directly used as a bio char/fertilizer. The produced
bio-crude may not be directly used as an alternate which requires
further hydrotreatment for commercial utilization. However, compli-
cated reaction mechanism is not required for the upgrading procedure
as the bio-crude obtained through HTL is less in moisture, oxygen
content and hence the fine hydrotreatment will enhance the quality of
bio-crude. Finally, the amount of the heat generated through the entire
process can be efficiently utilized to operate the hydrothermal gasifier
that refines the process economy.
3.4.2. HTL of wet/algal biomass
The major benefit of processing algae/wet biomass is the potential
for recycling of nutrients back to cultivation. The procedure of treating
wet biomass is similar to that of treating lignocellulose with a few
modifications. The schematic of the procedure treating the wet/algal
feedstock is presented in Fig. 3 adopted from Biller and Ross [148].
Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx
The major difference lies in treating the wet feedstock compared to dry
feedstock is ignoring the pre-treatment step.
Generally, pre-treatment is essential as the particle size of the micro
Pyrolysis
algae is quite small compared to lignocellulose that eliminates the
58 complexities of pumping slurries to the reactor. Further, dewatering
procedure at harvesting step tends to produce the feedstock slurry with
36 20% solids. Then the slurry is passed through the HTL reactor yields
29
24.8
bio crude that has to be hydro-treated further to produce hydrocarbon
22.6 fuels. During the HTL process the aqueous phase generated is
59 recirculated back to the algae cultivation procedure, CO2 that is
released can be utilized in the process of photosynthesis in the growth
of algae for next batch. During hydrotreatment the nutrients are
separated that are sent back to the algae cultivation procedure. This
overcomes the shortfalls of the HTL process economy.
4. Energy efficiency of HTL process
The ultimate target of the hydrothermal liquefaction procedure is to
convert the biomass to bio crude that can be utilized as an alternate to
the commercial fossil fuels. However, the economy of the process is
highly questionable due to the utilization of higher pressure conditions.
Fig. 4 describes the utilization of various product streams that can
affect the energy efficiency in terms of materials and feedstock. HTL of
wet biomass i.e., algal feedstock is a multifaceted processing technique
that can generate the nutrients which can be recycled for the growth of
algae, waste water can be used for the water requirements and CO2 for
the photosynthesis reaction.
It has the potential to bottleneck the current algal refining
procedure including consumption of water, fertilizer and energy input.
One of the cutting edge benefits of this HTL process is it consumes 10–
15% of the energy in the feedstock biomass yielding energy efficiency of
85–90%. HTL can recover more than 70% of the feedstock carbon
content that can be utilized for the carbon capture procedures. The
other technical edge of this process is the bio-crude that is obtained
from this process doesn’t require much treatment/upgrading proce-
dures for the commercial utilization. From Fig. 4, it is seen that several
by-products are obtained through this HTL process like fertilizer in the
form of a solid content, bio crude alternate to fossil fuels, the processed
water can be treated for the utilization and the nutrient cycle for the
11
A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Table 4 conventional crude oil. Briefly, this article enlightened the elemental
Major product compounds of bio-oil obtained by HTL process. composition of bio-crude obtained by HTL, different types of feedstock
adopted for HTL, mechanism of HTL processes, possible process flow
Product compounds Reference
diagrams for HTL of both wet and dry biomass; advantages/disadvan-
Monoaromatics tages and energy efficiency of the process. Finally, challenges still
Phenol Duan and Savage [158] subsist with this field which could serve as future scope for concerned
Benzene/Toluene/Styrene Ross et al. [75]
researchers. A very few of these challenges are listed below:
Cholesterol and Cholestene Jena and Das [77]
Vitamin E Zou et al. [76]
Fatty Acids 1. Set up an HTL pilot plant by analyzing the effects of feedstock (wet
Myristic acid Brown et al. [159] biomass) conversion efficiency.
Palmitic acid Shuping et al. [160] 2. Analyze the complexities of the critical parameters like temperature,
Steric acid/oleic acid Valdez et al. [161]
pressure and the residence time for HTL of a given feedstock.
Tetradecanoic and Octanoic acid Biller and Ross [40]
Hexadecanoic acid Jena et al. [162] 3. Examine possible pathways for optimized conversion via HTL (of
Arachidic acid Duan and Savage [158] both wet and dry biomass feedstock and their mixtures).
Eicosapentaenoic acid Brown et al. [159] 4. Explore the relationships between bio-crude oil yield and value
Alkane/Alkene
added chemical species and study the effects of catalyst on produc-
Hexadecane/hexadecane Yang et al. [163]
Heptadecane/Heptadecene Biller and Ross [40] tion of individual specific chemical compounds.
Pentadecane/Pentadecene Zou et al. [76] 5. Investigate the reaction pathways of HTL process of model com-
Phytane/Phytene Shuping et al. [160] pounds as well real biomass.
Docosane and Cholestane Valdez et al. [161] 6. Develop theoretical, especially computational fluid dynamics based,
Cycloalkane Anastasakis and Ross [24]
models to analyze the complex inherent properties like thermody-
Eicosane, Coprostane, Triconate, Hentriaconate, Duan and Savage [158]
Dotriaconate namic properties of the bio-crude, viscosity effects etc. so that to
Polyaromatic compounds optimize the processing parameters.
Naphthalene Yang et al. [163]
Quinoline Jena et al. [162]
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