Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

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Renewable and Sustainable Energy Reviews

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A review on hydrothermal liquefaction of biomass CrossMark

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

ARTICLE INFO ABSTRACT

Keywords: The rapid depletion of conventional fossil fuels and day-by-day growth of environmental pollution due to extensive use of fossil fuels have raised
Wet biomass concerns over the use of the fossil fuels; and thus search for alternate renewable and sustainable sources for fuels has started in the last few decades.
Dry biomass In this context biomass derived fuels seems to be the promising path; and various routes are available for the biomass processing such as pyrolysis,
Hydrothermal liquefaction transesterification, hydrothermal liquefaction, steam reforming, etc.; and the hydrothermal liquefac- tion (HTL) of wet biomass seems to be the
HTL mechanism Value-added promising route. Therefore, this article briefly enlightened a few concepts of HTL such as the elemental composition of bio-crude obtained by
chemicals Energy efficiency HTL, di fferent 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 by pyrolysis of lignocellulose biomass. Several statistics related to

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 production
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
Available online 08 June 2017
1364-0321/ © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/BY/4.0/).
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 81 (2018) 1378-1392
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 ofnitrogen 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 ofthe excess content
ofthe 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 81 (2018) 1378-1392

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]
Laurel algae 48.97 6.38 3.02 41.63 10.53 9.95 19.77 Ertas and Alma [53]
100

1.2.1.1 Cellulose 1.2.2.1 Lipids/Fats

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 Wet biomass feedstock
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, 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

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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 ofHTL of sewage
sludge operating at temperature of300 °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 ofHTL mechanisms is largely
qualitative and indicative although efforts have been made 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
1382
Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392
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
 A.R.K. Gollakota et al.
Table 2
Summary of literature pertained to hydrothermal liquefaction of biomass (both wet and dry).

S. No Author Description Feed Process conditions Products

Alhassan et al. [96]
1
2 Anastasakis and Ross
[24]
3 Bach et al. [23]
Hydrothermal liquefaction of de-oiled Jatropha curcas cake using deep eutectic De-oiled Jatropha curcas cake Temp: 250 °C HHV values of the HTL bio oii is 25.01 MJ/kg.
solvents (DESs) as catalyst and co solvents Pressure: 4.5 MPa
Reactor: Batch
Hydrothermal liquefaction of four brown macro algae commonly found on the UK Digitata, hyperborea, saccharina, Temp: 350 °C High nitrogen content is observed from the bio oii obtained indicating the
coasts: An energetic analysis of the process and comparison with bio-chemical esculenta Pressure: necessity for upgradation.
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:
Mufile furnace

4 Barriero et al. [10]
5 Caporgno et al. [11]
6 Chan et al. [105]
Hydrothermal liquefaction of microalgae: Effect on the product yields of the Nannochloropsis gaditana, Organic solvent dichloromethane increases the yield of biocrude at higher
Temp: 350 °C
addition of an organic solvent to separate the aqueous phase and the biocrude oii Scenedesmus almeriensis Pressure: 2 MPa oxygen and nitrogen contents.
Reactor: Micro
autoclave
Hydrothermal liquefaction of Nannochloropsis Oceanica in different solvents Nannochloropsis Oceanica Temp: 240-300 °C Alcohol co solvents yield high bio oii -60%.
Pressure: 32-
43 bar
Reactor: Batch
Effect of process parameters on hydrothermal liquefaction of oii palm biomass for Raw? fruit bunch, palm Mesocarp fibre Temp: 330-390 °C Optimum bio oii yield is obtained at 390 °C and 25 MPa
bio-oil production and its life cycle assessment and palm kernel shell Pressure: 25- 35 MPa
Reactor: Batch

7 Chen et al. [18] Hydrothermal liquefaction of mixed culture algal biomass from waste water Feedstock from One water INC. Temp: 260-320 °C HHV values of 33.3 MJ/Kg is viable with hydrocarbons, fatty acids, cyclic
treatment system into bio-crude oii Indianapolis Pressure: 1 MPa Reactor: amines.
1383

Batch
8 Costanzo et al. [97] Effect of low temperature hydrothermal liquefaction on catalytic Sorokiniana, minutissima, bijuga Temp: 225 °C Bio oii with similar composition to gas oii obtained via HTL/HDO process
hydrodenitrogenation of algae bio crude and model macromolecules Pressure: 20.7 bar Reactor: using Ru/C catalyst.
Batch
9 David et al. [106] Review and experimental study on pyrolysis and hydrothermal liquefaction of Nannochloropsis Temp: 250 °C Algal HTL is very handy when compared to pyrolysis in terms of yield.
microalgae for biofuel production. Pressure: 10-
25 MPa
Reactor:
Continuous

Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

10 Eboibi et al. [107] Hydrothermal liquefaction of microalgae for biocrude production: improving the Tetraselmis, Spirulina Temp: 300-350 °C The highest HHV of 40 MJ/kg w?as obtained after the process for the
biocrude properties with vacuum distillation Pressure: 30 bar Reactor: specified feedstock.
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 potențial biocrude oii Cyanophyta Temp: 370 °C High temperatures favoured phenols, benzenes, alkanes and fatty? acids
production and component analysis Pressure: 1.5Psi and low? temperatures favoured alkanes and heterocyclic compounds.
Reactor: Batch
13 Haarlemmer et al. [109] Analysis and comparison of bio oils obtained from hydrothermal liquefaction and Beech w?ood Temp: 300 °C High iodine value bio oii is obtained
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 subcritical Oii mill waste water Temp: 200-300 °C A maximum yield of 58 wt% w?as achieved having majority content of
conditions Pressure: 190 bar Reactor: phenolics.
Batch
15 He et al. [15] Continuous hydrothermal liquefaction of macro algae in the presence of organic Oedogonium Temp: 300-350 °C Presence of co solvent has minor effect on the product yield.
co-solvents Pressure: 10 bar Reactor:
Batch
Hietala et al. [95] A quantitative kinetic model for the fast and isothermal hydrothermal liquefaction Nannochlorosis Sp Temp: 100-400 °C Bio crude yield as high as 46% is achievable at 400 °C and 1 min residence
16 of Nannochlorosis Sp Pressure: 400 bar time.
(continued on next page)
 Table 2 (continued)

A.R.K. Gollakota et al.

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.
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 Reactor: yielding 18% diesel fraction.
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 Năzări 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
1384

Reactor: Stirred catalyst.

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 Reactor: higher biocrude produced
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

Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

Rosendahl [116] liquefaction of lignocellulosic systems Pressure: 300 bar Reactor: aromați cs.
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 Cg-Ci2 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] Tempera ture 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 oii with heating value of 37 MJ/kg is obtained which is
of algae Isochrysis Pressure: 35Psi equivalent to heavy crude oii.
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 (continued
Bio oii yield of 17% and 78% conversion with ether on next page)
soluble bio-oil
Pressure: 6-9 MPa under O2 environment.
 Table 2 (continued)

A.R.K. Gollakota et al.

S. No Author Description Feed Process conditions Products

Reactor: Autoclave
33 Sudasinghe et al. Hydrothermal liquefaction oii 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.
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 lowlipid 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 operațional 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.
1385

Reactor: Batch
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 oii yield, higher
sub criticai water for oii: product distribution Pressure: 2-5 MPa conversion rates.
Reactor: Batch
41 Xu and Etcheverry Hydro liquefaction of woody biomass in sub and super criticai 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 potențial for preparation of bio-

Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

production over Ce/HZSM-5 Pressure: oii 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 oii of
weed and the influence of the extraction solvents Pressure: 5 kPa Reactor: 26%.
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 oii is formed
bio-oil production Pressure: 0.5-
2 MPa
Reactor: Autoclave
45 Yim et al. [129] Metal oxide catalysed hydrothermal liquefaction of Malaysian oii palm Malaysian oii palm Temp: 390 °C The presence of phenols, ketones, aromatic carboxylic acids are
biomass to bio-oil under super criticai 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: - (continued on next page)
Reactor:
Batch
A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

process. Tian et al. [156] presented review on HTL from algal prospective
for algal biorefinery including the factors such as feedstock 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 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. 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 briefly reviewed the elemental composition of bio-crude obtained by
HTL, different types of feedstock adopted for HTL, mechanism of HTL
o £ xr
processes, possible process flow diagrams for HTL of both wet and dry
o
75 OI biomass and energy efficiency of the process. In addition, this article also
enlisted a possible future research scope for concerned research- ers.
w -Q
ț? W ° <£ PI
G 4> G
<DS-MP<V
S-M
H PiP«K f-l P-l
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.
Briefly, biomass is decomposed and depolymerized in to small com-
pounds. These compounds may be highly reactive, thus polymerizing 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 the components from
the different phases may vary accordingly. Since biomass is a complex
mixture of carbohydrates, lignin, proteins, and lipids, the reaction chemistry
and mechanisms of biomass liquefaction are consequently also complex
[135,136]. Fig. 1 presents the schematic overview of the reaction pathway
and the details of the steps are enlisted [137].

3.1. Depolymerisation of the biomass

Depolymerisation of biomass is a sequential dissolving of macro-

>, P<
<U molecules through utilization of their physical and chemical properties. The
OT intrinsic hemicellulose and cellulose biopolymers contributes positively
3 towards the thermal stability of the biofuel [138]. Depolymerisation process
overcomes the difficulties and obstinate properties of lignocellulose
biomass that mimics the natural geological processes of producing fossil
& I '-< fuels. The decisive parameters tempera- ture and pressure changes the
_P structure of the long chain polymers consisting of hydrogen, oxygen, and
c3 P<
carbon to shorter chain hydro- carbons [139]. Further, the energy contents
s£ of the organic materials are recycled in the presence of water.
>. s? eS T3
ffi £ £ >• £ 3.2. Decomposition of the biomass monomers by cleavage,
-a dehydration, decarboxylation and deamination

This step involves the loss of water molecule (dehydration), loss of CO2
molecule (decarboxylation) and removal of amino acid content
Table 2 (continued)

(deamination) [140]. The dehydration and decarboxylation facilitate the

removal of oxygen from the biomass in the form of H 2O and CO2
respectively. Biomass comprising macromolecules are hydrolysed to

1386
A.R.K. Gollakota et al.
Water-dissolved
Biomass
materials
degradation
Polymerization
Fig. 1. Reaction pathway of the hydrothermal liquefaction.
Fig. 2. Process flow diagram of HTL process of lignocellulose biomass adopted from Biller and Ross [148].
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 compound [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
1387
Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392
degradation
Polymerization
Hydrocarbon Fuels
Hydrotreating -► Hydrocarbon Fuels
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
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].
The major difference lies in treating the wet feedstock compared to dry
Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392
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 bio
29 crude that has to be hydro-treated further to produce hydrocarbon fuels.
24.8
22.6
During the HTL process the aqueous phase generated is recirculated back
59 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
Table 4
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A.R.K. Gollakota et al. Renewable and Sustainable Energy Reviews 81 (2018) 1378-1392

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