Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

An overview of effect of process parameters on hydrothermal carbonization MARK

of biomass
⁎
Sabzoi Nizamuddina, , Humair Ahmed Balochb, G.J. Griffina, N.M. Mubarakc,⁎⁎, Abdul
Waheed Bhuttob, Rashid Abrod, Shaukat Ali Mazarib, Brahim Si Alie
a
School of Engineering, RMIT University, Melbourne, 3001 Australia
b
Department of Chemical Engineering, Dawood University of Engineering and Technology, MA Jinnah Road, 74800, Karachi, Pakistan
c
Department of Chemical Engineering, School of Engineering and Science, Curtin University, 98009 Sarawak, Malaysia
d
Engineering Services Center, Karachi Laboratories Complex, Pakistan Council of Scientific and Industrial Research, Karachi, Pakistan
e
Department of Chemical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

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

Keywords: The preceding decades witnessed hydrothermal processes being actively utilized all over the world, specifically
Process parameters in the developed zones. Their optimum usage is primarily sought for in terms of conversion of biomass into
Hydrothermal carbonization valuable solid, liquid and gaseous fuels. Indeed, Hydrothermal carbonization (HTC) is an effective and
Catalyst environment friendly technique; it possesses extensive potential towards producing high-energy density solid
High-energy solid fuel
fuels. However, the production and quality of solid fuels from HTC depends upon several parameters;
temperature, feed type, residence time, pressure and catalyst being the eminent ones.
This study investigates the influence of operating parameters on solid fuel production during HTC. The
biomass quality has also been analyzed in HTC by extending existing literature work through experiments that
have been performed. Data including chemical composition, heating value, proximate analysis and ultimate
analysis for different types of biomass was consequently collected and analyzed. It was found that reaction
temperature, residence time and type of feed material are the primary factors that influence the HTC process. At
higher temperatures, lower solid product is obtained; the carbon content increases, whilst the hydrogen and
oxygen content decrease. Further, it has been found that higher lignin content in biomass leads to an increased
solid fuel production.

1. Introduction greenhouse gases (GHG) pre-eminently carbon dioxide (CO2), nitrogen

Before the emergence of a fossil fuel based economy in the 19th
century; biomass was the primary source serving as an integral
contributor towards energy production. However, the realm of reduced
energy output from biomass readily replaced the latter with fossil fuels
along with increased acceptance. Further, fossil fuels also committed to
serve as a cost effective and a feasible alternate for the world at large.
The passage of time to date witnessed a rise in demand of energy
due to an escalated growth in population and industrialization world-
wide. The persistence of rapidly emerging new economies in the
forthcoming decades is speculated to add apprehension to the existing
gap between demand and supply. It is henceforth a consequence that
concerns have apparently reached a pivotal point whereby it is
anticipated that the fossil fuel energy will not be able to fulfil the
demand. Further, environmental problems imposed by the liberation of
oxide (NOx) and particulate matter by utilization of fossil fuels
continue to remain factors of concern [1]. As stated by the
International Maritime Organization (IMO), there exists a need to
reduce more than 80% of the engine-out NOx. The latter is supported
by Fig. 1 that shows the emission of CO2 from fossil fuels and highlights
a drastic increase of CO2 in the atmosphere. To further jeopardize the
situation unbalanced market prices, and limited fuel availability [2–6]
add to the drawbacks that deviate from the support of utilization of
fossil fuels. It is therefore foreseen that a shift backwards towards a
biomass-based economy is more than just envisioned. The world at
large is being observed to be ushering towards alternates as an
obligatory option. In terms of the subsets of latter biomass promises
itself as being one of the few existing viable means of renewable energy
resources that is capable of transformation into solid, liquid and
gaseous fuels [7]. At present biomass is a rich source of energy

⁎
Corresponding author.
⁎⁎
Corresponding author at: Department of Chemical Engineering, Faculty of Engineering and Science, Curtin University, 98009 Sarawak, Malaysia.
E-mail addresses: nizamuddin248@gmail.com (S. Nizamuddin), mubarak.yaseen@gmail.com, mubarak.mujawar@curtin.edu.my (N.M. Mubarak).

http://dx.doi.org/10.1016/j.rser.2016.12.122
Received 21 December 2015; Received in revised form 13 December 2016; Accepted 26 December 2016
Available online 24 February 2017
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.
S. Nizamuddin et al.
Fig. 1. Emission of carbon dioxide (CO2) [141].
Fig. 2. Biomass resources present for utilization [9].
available from agriculture, forests and energy crops [8]. Fig. 2 shows
biomass resources that are theoretically existent; it reveals that most of
the biomass comes from agricultural land [9].
Biomass is a biological matter that incorporates all living matter on
the earth. Biomass mainly consists of cellulose (C6H10O5)x, hemicellu-
loses (C5H8O4)m, lignin [C9H10O3(COH3)0.9-1.7]n, small extractives
[10,11], fats, proteins [12], sugars, arrowroots, water, ash, besides
additional mixtures. The largest fraction of biomass is cellulose, which
is 35–50% of biomass by weight. Hemicelluloses contains 20-35% of
biomass by weight, lignin shares about 15-20% of biomass weight
whilst the remaining 15-20% includes proteins, fats, extractives and
ash content as shown in Fig. 3 [13]. The general classification of
biomass with sub-groups is shown in Table 1. Biomass is characterized
by its physical properties, proximate analysis and ultimate analysis
[14]. These properties tend to change in every substance [15] with the
growth environment [16], time and age [17,18]. Table 2 gives the
ultimate analysis, proximate analysis and heating value (HHV) of
Fig. 3. Typical composition of biomass.
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Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299
different types of biomass. HHV is calculated by using the following
equations.
HHVI = 196/1000 (FC) + 14119/1000 (1)
HHVII = 312/1000 (FC) + 1534 /10000 (VM) (2)
Values for fixed carbon (FC) and volatile matter (VM) are taken
from the Table 2.
Biomass has proven itself as not only being an efficient source of
energy but also as a key component towards enhancing the workability
of biofuels in comparison to non-renewable petroleum products.
Simultaneously, biomass reduces deterioration of the environment by
equating the CO2 amount released to the amount that is absorbed via
photosynthesis. Annual growth of biomass (dry basis) is 118x109 tons
on the continent basis [19]. International energy agency (IEA) states
that the entire oil consumption over the world in 2007 amounted to be
3.53x109 tons that is equivalent to 148.26x1018 J of energy, which
however is 10% lesser than the worldwide per annum growth of
biomass in relation to the energy content [20]. On the other hand,
one of the investigations by United Nations Conference on environ-
ment and development (UNCED) shows that biomass is speculated to
supply energy globally to approximately 50% of the existing principal
energy requirement by 2050 [21]. Production of biofuels and chemicals
from biomass can play a vital balanced befitting addition to the world
in terms of provision of cheap transportation, electricity, and chemicals
such as bio-fertilizers, bio-plastics, and bio-polyesters [22]. It is there-
fore speculated that an adequate optimum utilization of such meth-
odologies of relevance promises a dimension that extends beyond the
sets of research, social and economic activities in terms of minimizing
the interdependence on fossil fuels.
Biomass offers itself as an attractive feed for biofuels for three
reasons at large. First and foremost, it is a renewable source. Hence, in
comparison to fossil fuels, it offers the options for developments in near
future and serves as an everlasting solution. Secondly, it releases CO2
in fewer amounts coupled with lesser sulfur content. Hence, it is clearly
an environmentally friendly source of energy and fuel. Third, it
possesses economic potential under the scenario whereby prices of
petroleum fuels rise in near future [23]. Furthermore, similar to fossil
fuels, biomass promises a position as a feedstock for the production of
valuable chemicals in industries. Jacob and Igor [24] consider that the
energy consumption in the chemical sector is around 10% of the global
consumption of energy.
There exist a range of fuels that can be produced from biomass
sources. These extend from gaseous fuels including hydrogen and
methane to liquid fuels such as biodiesel, fischer tropsch diesel,
vegetable oil, bio-alcohols (ethanol and methanol), biosynthetic oil
[25] and solid fuel such as biochar and hydrochar. Biofuels can be
classified as either primary or secondary fuels. Primary fuels are
natural and unprocessed fuels. Primary fuels are made to undergo
combustion directly for both heating and cooking purposes. Examples
of primary fuels include firewood, wood chips, and pallets. Secondary
fuels are derived from primary fuels via a wide variety of processes.
These fuels have various applications in transport and industrial
process [26]. Additionally, due to environmental benefits depicted by
biofuels, the share of biofuels is committed to increase in the
transportation sector with time. Biofuels beehive more advantages
than fossil fuels in multiple aspects namely the availability of sources
and lower emission of CO2. Hence, biofuels are environment-friendly
fuels; they promise energy security, foreign exchange savings, rural
development, sustainability and biodegradability [27,28]. However, the
main underlying difference between biofuels and petroleum fuels lies in
the amount of oxygen content present in either which is also
accountable for making their properties widely differ. Biofuels contain
10-45% oxygen, whereas petroleum products have none. However, in
order to support biofuels numerous studies have been recently
conducted to justify their social and environmental effects and benefits
S. Nizamuddin et al. Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299

Table 1
Classification of biomass [111].

Biomass group Biomass sub groups, varieties and species

Wood and woody biomass Coniferous or deciduous; angiospermous or gymnouspermous; soft or hard; stems, branches, foliage, bark, chips, lumps,
pallets, sawdust, briquits, sawmill and various wood species
Herbaceous and agricultural biomass Annual and perennial and field based or process based. Such as grasses and flowers, straws and other residues
Aquatic biomass Marine or fresh water algae; macroalgae or microalgae, seaweed, kelp, lake weed etc
Animal and human biomass waste Bones, meat-bone meal, chicken liter and manures etc
Contaminated biomass and industrial biomass waste Municipal solid waste, demolition wood, refuse-derived fuel, sewage sludge, hospital waste, paper-pulp sludge,
(semi-biomass) chipboard, fiber, plywood, wood pallets and boxes, railway sleepers etc
Biomass mixtures Blends from above varieties

[29–39].
In this study, an overview on the effect of operating parameters on
yield as well as on the quality of the hydrochar produced from
hydrothermal carbonization (HTC) process is highlighted. Further,
there is a critical discussion on the effect of conversion of biomass into
solid fuels with their compositions being consequently evaluated.
Furthermore, composition and characterization of different biomass
are discussed. Conclusions are drawn in the light of literature; with
recommendations being henceforth provided.
2. Hydrothermal carbonization (HTC) process
The HTC process is an environment friendly technology. It ther-
mally converts a variety of biomass feedstocks into high carbon content
containing, smokeless solid fuels [40,41]. HTC of biomass is studied
along with water by application of higher temperatures (180–250 °C)
at elevated pressure (2-10MPa) for several hours [38]. It was Bergius
and Specht [42] who introduced HTC process for the first time. They
converted cellulosic material into high carbon material. The mixture of
cellulose and water was heated in a closed vessel at 250–310 °C. As a
result, the solid with lower O/C ratio was produced suggesting HTC as
a successful conversion process. This was followed by further modifica-
tions and improvements in HTC processes that were carried out by Berl
and Schmidt. They studied various saccharides at 150–35 0 °C [42].
Through relevant studies conducted since the last decade, HTC has
emerged as a promising technology due to its inherent benefits [43–47]
such as conversion of biomass into numerous products. Studies have
also shown a consideration of biomass as a solid fuel that is comparable
to brown coal [32,43–49], a source of bio-oil [22,50–53], soil amend-
ment to improve fertility of soil and crop yields [48,54–56], as an
activated carbon material that can be used as an adsorbent for water
purification systems or CO2 sorption [54], and as a low-cost adsorbent
or permeable reactive barrier for Uranium (VI), Copper and cadmium
contaminated waters [57,58], carbon material with nanostructure
[54,59,60], carbon catalyst which can be used in the production of
fine chemicals [38], and lastly a carbon material that can enhance fuel
cells efficiency [54]. Fig. 4 shows the schematic diagram of HTC with
some of the possible applications of hydrochar [61]. The HTC process
may be classified as either Direct HTC or Catalytic HTC process. In
Direct HTC process, only water and feed are heated in a reactor at
different temperature ranges in the absence of a catalyst, whereas in
catalytic HTC process, a catalyst is used. HTC yields solid, liquid, and
gaseous products [32]. The product distribution is primarily dependent
on the feedstock and process temperature. However, there does exist
an influence of the reaction time and the biomass to water ratio
[52,53,62,63].
Presence of water accelerates the carbonization process of biomass
and simultaneously affects the product distribution [32,64,65]. The
reason for the latter is self-evident; water in biomass serves as both a
reacting medium and a reactant [66,67]. Thermodynamically, water is
a completely oxidized composite that is not capacitive of a high heating
value. Hence, water serves as a perfect reaction agent with the capacity
to conduct such types of reactions in contrast to the pyrolysis reactions.
In pyrolysis process, the water content present in biomass has negative
effect on the process because it requires higher heat of vaporization
[22]. HTC therefore increases the options of biomass usage as a
feedstock together with the overall process economy. It is also
capacitive of the overall energy used for it caters the moisture content
problem as it uses drying. At hydrothermal water conditions, nitrogen
atoms present in biomass are converted to N2O; while phosphorous,
chlorine and sulfur are oxidized to their respective inorganic acids
which are simultaneously neutralized with the addition of a suitable
base [68].
Biomass normally contains 40–60% oxygen. This is the reason why
the exclusion of oxygen from biomass serves as the most important
objective to increase energy density. Oxygen may be removed from feed
biomass either by dehydration (oxygen is eliminated from the biomass
feed in the form of water) or by decarboxylation (oxygen is removed in
the form of carbon dioxide). Biomass experiences hydration reactions
at higher temperatures and pressures, even in excess of water [19]. It
undergoes depolymerization reactions via hydrolysis at elevated tem-
peratures because of high ionization of water at those temperatures
[69]. At the same time, both acidic and basic nature [66] of water
justify the capability of hydrolysis to change biomass into biofuels
directly. This is elaborated further by adding the credibility of HTC
delivering quantities greater than those in comparison to the pyrolysis
process that does not involve water [70]. A complete overview of the
aforementioned is detailed and discussed later. The basic nature of
water weakens certain bonds in the organic material. As a result, new
molecular fragments are generated which amend the reaction environ-
ment. At the same time, water acts as an acid catalyst, speeding up
different reactions. A review of previous studies on a different type of
biomass using HTC process at different parameters is given in Table 3.
3. Process parameters
HTC process requires knowledge of the effect of process para-
meters; reaction temperature, feedstock, reaction time, catalyst and
pressure. The effects of each process parameter are further discussed in
the following section.
3.1. Effect of temperature
Temperature is suggested as the key parameter for HTC process.
The elementary role of temperature is to offer heat of disintegration for
fragmentation of the biomass bond. Variations in the yields of the
processes describe and measure the competency of temperature to
crumble the biomass. Effectiveness of biomass conversion increases
with an increase in temperature. This is generally because of additional
energy being delivered by the temperature to break the biomass bonds
[71]. The main products of HTC process are gas, liquid and solid
products. Usually, moderate temperatures favour oil yield, whereas
higher temperatures generate gas and the char products dominantly.
This can be achieved both by secondary decomposition and bourdard
gas reaction in which gas formation is more favourable [72,73] or even
by the recombination of free radical reactions where a greater amount

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Table 2
Characterization of various types of biomass.

Biomass type Proximate analysis Ultimate analysis Heating value References

FC VM Ash C H O HHV I HHV II

Rice husk 16.95 61.81 21.24 38.5 5.2 34.61 17.44 14.77 [112]
Sal seed husk 28.06 62.54 9.4 48.12 6.55 35.93 19.62 18.35 [112]
Olive husk 18.4 77.5 4.1 49.9 6.2 42.0 19.23 18.93 [113]
Peanut hull 21.09 73.02 5.89 45.77 5.46 39.56 18.25 17.78 [114]
Hazelnut shell 28.3 69.3 1.4 52.9 5.6 42.7 19.67 19.46 [113,114]
Brazil nut shell 22.2 76.1 1.7 49.15 5.7 42.8 18.47 18.60 [115]
Akhrot shell 18.78 79.98 1.2 49.81 5.64 42.94 17.80 18.13 [112,116]
Coconut shell 22.1 77.19 0.71 50.22 5.7 43.37 18.45 18.74 [112,116]
Pistachio shell 16.84 82.03 1.13 48.79 5.91 43.41 17.42 17.84 [114]
Groundnut shell 21.6 72.7 5.7 48.59 5.64 39.49 18.35 17.89 [112,114]
Chapparal wood 18.68 75.19 6.13 46.9 5.08 40.17 17.78 17.36 [112]
Spruce wood 29.3 70.2 1.5 51.9 6.1 40.9 19.86 19.91 [117]
Ailanthus wood 24.8 73.5 1.7 49.5 6.2 41 18.98 19.01 [117]
Beech wood 24.6 74 0.4 49.5 6.2 41.2 18.94 19.03 [117]
Bamboo wood 11.24 86.8 1.95 48.76 6.32 42.77 16.32 16.82 [112]
Red wood 19.92 79.72 0.36 50.64 5.98 42.88 18.02 18.44 [91]
Douglas fir wood 12.6 87.3 0.1 50.64 6.18 43 16.59 17.32 [112]
Casurina wood 19.58 78.58 1.83 48.5 6.24 43.12 17.96 18.16 [116]
Neem wood 12.19 85.86 1.93 48.26 6.27 43.46 16.51 16.97 [112]
Subabul wood 18.52 81.02 1.2 48.15 5.87 44.75 17.75 18.21 [116]
Wood Bark 31.8 66.6 1.6 53.1 6.1 40.6 20.35 20.14 [117]
Douglas fir bark 32.79 65.46 1.75 53.1 6.1 40.6 20.55 20.27 [118]
Wood chips 23.5 76.4 0.1 48.1 5.99 45.74 18.73 19.05 [114]
Mulberry stick 22.8 75.1 2.1 44.23 6.61 46.25 18.59 18.63 [119]
Peach pit 19.8 79.1 1.1 49.14 6.34 43.52 18.00 18.31 [119]
Pine needles 26.12 72.38 1.5 48.21 6.57 43.72 19.24 19.25 [117]
Sena leaves 25.5 57.2 17.3 36.2 4.72 37.49 19.12 16.73 [114]
Coconut fibre 26.6 70.6 2.8 46.43 5.49 43.78 19.33 19.13 [117]
Coconut coir 29.7 66.58 3.72 50.29 5.05 39.63 19.94 19.48 [117]
Corncob 11.5 87.4 1.1 49 5.4 44.5 16.37 17.00 [113]
Tea waste 13 85.5 1.5 48 5.5 44 16.67 17.17 [113]
Walnut shell 37.9 59.3 2.8 53.4 6.6 45.4 21.55 20.92 [113]
Sunflower shell 19.8 76.2 4 47.4 5.8 41.3 18.00 17.87 [113]
Rice straw 15.55 61.1 15.25 38.52 6.13 39.28 17.17 14.22 [120]
Wheat straw 14.96 63.96 12.45 42.11 6.53 40.51 17.05 14.48 [120]
Corn straw 14.83 62.74 13.12 42.69 6.16 42.69 17.03 14.25 [120]
Soya bean 15.62 68.95 6.08 43.16 6.9 44.76 17.18 15.45 [120]
Corn cob 15.8 70.24 7.5 44.53 6.89 45.97 17.22 15.70 [120]
Cotton stalk 18.57 67.63 6.41 46.1 6.85 43.35 17.76 16.17 [120]
Cotton shuck 20.74 62.16 6.88 44.54 6.6 46.66 18.18 16.01 [120]
Peanut stalk 15.66 66.67 9.12 40.28 7.18 42.47 17.19 15.11 [120]
Peanut shuck 16.85 61.64 12.15 45.9 6.74 42.79 17.42 14.71 [120]
Sesame stalk 17.3 68.93 6.11 41.34 6.57 45.16 17.51 15.97 [120]
Broad bean stalk 18.9 68.44 5.03 42.16 6.13 45.28 17.82 16.40 [120]
Rape stalk 17.26 72.99 3.6 42.42 7.06 46.1 17.50 16.58 [120]
Willow tree 15.55 69.2 6.17 46.79 7.1 40.6 17.17 15.47 [120]
Rubber plant 18.3 62.92 9.9 48.69 7.29 39.03 17.71 15.36 [120]
Poplar 15.42 74.04 2.63 47.46 6.74 44.5 17.14 16.17 [120]
Pine tree 14.45 76.5 0.89 49.41 7.67 42.19 16.95 16.24 [120]
Phoenix tree 18.29 68.68 5.28 48.14 7.88 39.84 17.70 16.24 [120]
Birch tree 13.68 74.91 2.36 48.32 8.36 40.6 16.80 15.76 [120]
Met sequoia 16.11 74.3 2.2 47.98 6.82 43.98 17.28 16.42 [120]
Coal 43.6 2.4 8.3 81.5 4 3.3 22.66 13.97 [121]
Red oak wood 21.5 78.6 0.5 50 6 42.4 18.33 18.77 [121]
Barley straw 4.8 78.5 9.8 41.4 6.2 51.7 15.06 13.54 [122]
Flax straw 8.8 80.3 3 43.1 6.2 49.9 15.84 15.06 [122]
Timothy grass 16 77.9 1.1 42.4 6 50.4 17.26 16.94 [122]
Pinewood 10.3 82.4 1.5 49 6.4 44.4 16.14 15.85 [122]
Pinuspinaster 14.1 85.8 0.2 48.4 6 45.3 16.88 17.56 [123]
Cedrusatlantica 16.7 82.9 0.4 50.3 5.6 43.6 17.39 17.93 [123]
Castaneasativa 20.3 79.6 0.1 47.1 4.9 47.7 18.10 18.54 [123]
Fogussylvatica 13.9 85.7 0.5 46.2 5.8 47.2 16.84 17.48 [123]
Quercusrobur 18 81.7 0.3 47.2 5.5 46.8 17.65 18.15 [123]
Prunusaviurn 15 84.9 0.4 48.6 5.8 45.3 17.06 17.70 [123]
Salix babilonica 16.8 80.8 2.4 47.2 5.6 44.4 17.41 17.64 [123]
Bowdichianitida 18.2 81.8 0.1 52.3 6.1 41.3 17.69 18.23 [123]
Hymenia courbaril 17.6 81.7 0.7 48.3 5.7 45.1 17.57 18.02 [123]
Wood pallets (pine) 14.5 80.4 0.2 45.5 6.6 47.7 16.96 16.86 [124]
Paper plant residue 19.5 60.5 13.5 33.8 4 39.1 17.94 15.36 [124]
Green house residue 5.5 61 31 47.1 7.4 10.9 15.20 11.07 [124]
Sunflower pellets 19.5 65.2 4.1 44.1 5.17 34.6 17.94 16.09 [124]
Olive cake pellets 15.7 64.2 8.2 42.1 4.99 31 17.20 14.75 [124]
(continued on next page)

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Table 2 (continued)

Biomass type Proximate analysis Ultimate analysis Heating value References

FC VM Ash C H O HHV I HHV II

Sewage sludge 7 44.6 41.5 52 6.3 32.1 15.49 9.03 [124]

Oil palm shell 15.75 77.91 6.34 51.1 6 42.9 17.21 16.87 [125]
Japanese apricot tree 12.2 87.72 0.08 49.6 5.9 44.5 16.51 17.26 [125]
Alfalfa Stalk 15.62 68.02 5.84 40.60 5.15 36.02 17.22 17.04 [126]
Urban wood waste 12.5 52.56 4.08 33.22 3.84 27.04 17.30 14.8 [126]
Switch Grass 12.19 65.19 7.63 39.68 4.95 31.77 16.93 16.24 [126]
Sawdust 9.34 55.03 0.69 32.06 3.86 27.04 17.27 17.63 [126]
Sugarcane bagasse 15.0 - 11.3 44.8 5.4 39.6 16.57 16.91 [113, 127]
Almond Shells 20.71 76 3.29 49.3 5.97 40.63 18.18 18.12 [113, 128, 129]
Almond Hulls 20.07 73.8 6.13 47.53 5.97 39.16 18.05 17.58 [128]
Olive Pitts 21.2 75.6 3.2 48.81 5.79 43.48 17.31 17.66 [114]
Willow wood 16.07 82.22 1.71 49.90 5.90 41.80 16.78 14.37 [130]
Hybrid poplar 12.49 84.81 2.70 50.18 6.06 40.43 17.54 18.04 [130]

Fig. 4. Schematic of HTC process for possible applications [61].

of char will be formed [22]. Effect of temperature on distribution of the Fig. 5. Yields of paper industry waste as a function of temperature [142].

yield of liquefaction product from paper industry waste is well defined

in Fig. 5, which shows that lower temperature favours maximum solid
production. As the temperature rises the solid production decreases
gradually, whilst the liquid and gaseous products increase. Generally,
solid product is dominant in the temperature ranges of 150–200 °C; at
moderate temperature ranges of 250–350 °C the liquid yield will be
higher, whereas above 350 °C, gas formation yield leads to solid and
liquid products.
Fig. 6 provides information about the variation in solid yields
produced from different types of biomass as a function of temperature
in HTC process. Results of studies conducted by Liu et al. [74] and Sun
et al. [75] demonstrated that the rates of solid products were very high
at temperatures below 200 °C. An increase in temperature to inter-
mediate range > 200–250 °C caused the solid product to decrease
alongwith another increase at temperatures > 280 °C. Carbonization at
lower temperatures produces a higher amount of solid. At a higher
temperatures carbonization is greater resulting in the formation of
more liquid and gaseous products along with lower solid products.
Extensive research work has been carried out to study the effect of
temperature on product distribution during HTC process [76–79]. The
biomass selected as a feed included enteromorphaprolifa, cattle
manure, Spirulinaplatensis and Cunninghamialanceolata. It was ob-
served that the solid product decreases as temperature increased. Chen
et al. [80] reported similar results for sugar cane bagasse. Liu et al. [81]
investigated the comparative effect of temperature from 150–375 °C on
two types of biomass; coconut fiber and eucalyptus leaves. They found
that the solid yield decreases rapidly with an increase in temperature to

Table 3
Review of hydrochar synthesis using HTC process.

Biomass feed type Temperature (oC) Reaction time Reactor type Solid yield % Reference

Mix wood 215–295 5–60 min Parr stirrered pressure reactor 50.1–69.1 [53]
Microalgae 190–210 30–120 min Parr stirrered stainless steel reactor 25.3–45.7 [50]
Olive mill wastewater 180, 220 840 min Lab-scale autoclave ~30 [131]
Empty fruit bunch 150–350 20 min Parr stirrered pressure batch reactor 49–76 [49]
Eucalyptus sawdust 250 120 min Autoclave reactor 40 [132]
Barley straw 37
Poplar wood 180–230 480 min Stainless steel autoclave 51.9–89.9 [133]
Olive residues 49.0–75.4
Wheat straw 53.7–80.1
Palm shell 180–260 30–120 min Amar autoclave batch reactor 38.7–63.0 [134]
Switchgrass 300–400 60–180 min Cylindrical metal container 35.2–82.0 [135]

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Fig. 6. Effect of temperature on solid yield during HTC of various biomass feed types
[72–74,76–79,81,143].
350 °C for both feed materials. However, from and beyond 350–
375 °C, solid yield reduces gradually. Lu et al. [82] further clarified
that the carbon distribution is also affected by temperature.
Temperature influences the characteristics of solid fuel produced by
HTC process. Jamari et al. [42] investigated the effect of temperature
on empty fruit bunch (EFB) during HTC. It was observed that the
carbon value increased with increase in temperature in contrast to
hydrogen and oxygen content. At higher temperatures, the oxygen and
hydrogen contents decreased validating the removal of these sub-
stances with temperature.
Additionally it is observed that higher temperatures during HTC
process increase the magnitude of aromatization of carbon structure.
Furthermore, the observation that materials undergo increased aro-
matization at high temperature is heavily attributed to the arrangement
of the hydrochar and aromatic structures with fewer reactive sites, less
abrupt decomposition and a well-organized hydrochar structure that
was supportably obtained under optimum conditions. Hence, the effect
of temperature is a vital role in the formation of hydrochar.
3.2. Effect of feedstock
The structure and composition of biomass types vary from each
other due to the difference of growing environment and growth time.
Major components of biomass are cellulose, hemicelluloses and lignin.
Every component behaves differently along with temperature varia-
tions. Generally, higher content of cellulose and hemicelluloses en-
hance the oil yield. Hindsight, it is also true that higher the content of
lignin in biomass the greater the char produced. This is because lignin
is hard to degrade due to its complex branching and thus remains as a
residue [68]. Under hydrothermal conditions, cellulose hydrolyzes
significantly above 200 °C [68], hemicelluloses at around 180 °C and
lignin degrades at around 200 °C [32]. Zhong et al. [83] investigated
the effect of lignin content present in four types of wood biomass
including Cunninghamialanceolata, Fraxinusmandshurica, Pinusma-
ssoniana, Lamb and PopulustomentosaCarr on the oil yield. The
experimental observation proved that higher lignin content results in
decreased bio-oil and increased biochar production. The oil yield was
reduced by repolymerization and cyclization of lignin fragments of
liquid oil [84]. Yang et al. [85] discussed the weight loss behavior of
cellulose, hemicelluloses, and lignin of lignocellulosic biomass. They
observed that 94.5% loss of cellulose, 80% of hemicellulose and 54.3%
loss of lignin at 400° C, 268° C, and 900 °C, respectively. This clearly
shows that the degradation of biomass with higher lignin content
produces more char [86]. Similar results were reported by Gani et al.
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Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299
[87] and Karagoz et al. [88]. The HHV of HTC-char is strongly
dependent on the initial composition of feed material. Berge et al.
[62] reported that the HHV of biochar produced from the waste paper
is 23.9 MJ/kg. HHV of the wood mixture was calculated by Hoakman
et al. [53] and it was found to fall between the range of 22.5–29.5 MJ/
kg. The HHV of sargassumhorneri is similar to HHV value of wood
waste and paper waste due to similar lignocellulosic composition of
paper waste, wood waste and sargassumhorneri [89]. Table 4 gives the
summary of lignocellulosic composition of different types of biomass.
The mechanism of HTC process includes decarboxylation, dehydration,
condensation polymerization, hydrolysis, and aromatization.
Understanding the nature of these mechanisms depends primarily
upon the type of biomass feed [32]. In general, the effect of feed
composition plays as a crucial parameter in the formation of hydro-
char. The precursor materials influence the pore size distribution in the
final product. The composition of lignin and cellulose content in the
precursor materials play a significant role in the porosity of hydrochar
produced during HTC process.
3.3. Effect of reaction time
HTC is recognized as a slow reaction. For HTC, the reported
reaction time varies from several minutes to a few days. Reaction time
however only influences the hydrolysis reactions up to a certain range
of time beyond which it does not have any specific impact on the
process. Generally, it is observed that a greater quantity of solid
product is obtained at higher reaction times. Reaction duration defines
the product composition as well as overall biomass conversion. Under
supercritical conditions, the hydrolysis rate and degradation of biomass
rate are relatively fast [90]. Hence, a comparatively smaller duration of
time is required to decompose biomass effectively. Various studies and
research have been conducted to examine the effect of reaction time for
solid, liquid or gaseous product. Boocock et al. [91] conducted a study
in which the results proved that longer reaction times are required for
increased bio-oil production with the exception of those that possess a
very high biomass to water ratio. Yan et al. [92] observed a slight
increment in bio-oil production with longer run times. Longer reaction
times support bio-oil yield and conversions of biomass to products at a
lower temperature (150 °C). At higher temperatures (250–280 °C)
however, the overall conversion and gaseous product rate increases
[93]. Effect of variation in run times on conversions showed that an
increase in time increases the conversion [94]. Zhang et al. [70]
observed that longer residence time supports gaseous and solid product
formation in contrast to liquid product formation. Further, residence
time affects the product composition also. According to Karagöz, et al.
[93] the products not only differ at shorter and longer run times; they
also differ at lower and higher temperatures (180 °C or 250 °C).
According to the results of experiments that have been previously
conducted using a short run time; the solid fuels produced have higher
heating values. This can be either due to the removal of oxygen present
in biomass or by hydrolysis of hemicellulose. Some studies carried out
at a lower run time (up to half of an hour) resulted in the production of
HTC solid with a heating value equal or greater than lignin [95,96]. The
reaction times influence the formation of hydrochar during HTC
process. During HTC process the higher the reaction time the greater
the formation of defined structure porosity, pore volume and high BET
surface area and vice versa.
3.4. Effect of pressure
Pressure is another factor which significantly influences the degra-
dation of biomass in hydrolysis process. Biomass decomposition and
hydrolysis rate can be controlled by keeping pressure above the critical
pressure of medium. This may significantly boost satisfactory reaction
routes that thermodynamically favour conversion of biomass to valu-
able products. Pressure has a positive effect on the density of solvent or
S. Nizamuddin et al. Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299

Table 4
Summary of composition of different types of biomass.

Fuel Cellulose Hemicellulose Lignin Extractive/ash References

Almond shell 50.7 28.9 20.4 2.5 [113]

Beech wood 45.3 31.2 21.9 1.6 [113]
White poplar 49.0 25.6 23.1 0.2 [1]
European birch 48.5 25.1 19.4 0.3 [1]
White willow 49.6 26.7 22.7 0.3 [1]
Corncob 50.5 31 15 3.5 [113]
Monterey pine 41.7 20.5 25.9 0.3 [1]
Douglas fir 42.0 23.5 27.8 0.4 [1]
Hazelnut shell 26.8 30.4 42.9 3.3 [113]
Olive husk 24 23.6 48.4 9.4 [113]
Spruce wood 49.8 20.7 27 2.5 [113]
Sunflower shell 48.4 34.6 17 2.7 [113]
Tea waste 30.2 19.9 40 9.9 [113]
Walnut shell 25.6 22.7 52.3 2.8 [113]
Wheat straw 28.8 39.4 18.6 3.3 [113]
Empty Fruit Bunch 26 43 24 7 [136]
Fiber 19 37 33 11 [136]
Shell 22 26 46 6 [136]
Hazelnut seed coat 29.6 15.7 53 1.4 [117]
Wood bark 24.8 29.8 43.8 1.6 [117]
Corn Stover 51.2 30.7 14.4 3.7 [117]
Tobacco stalk 42.4 28.2 27 2.4 [117]
Tobacco leaf 36.3 34.4 12.1 17.2 [117]
Ailanthus wood 46.7 26.6 26.2 0.5 [117]
Softwood (av.) 45.8 24.4 28 1.7 [117]
Hardwood (av.) 45.2 31.3 21.7 2.7 [117]
Waste material 50.6 29.2 24.7 4.5 [117]
Acacia Mangium 43.12 72.14 29.91 6.76 [137]
Bagasse 49.20 74.98 19.54 1.28 [137]
Bagasse pith 45.18 72.16 22.13 1.24 [137]
Coconut husk 30.55 56.45 38.82 2.65 [137]
Coconut shell 26.49 79.29 35.54 1.86 [137]
Corn stalk 42.43 68.18 21.73 3.27 [137]
Kenaf 42.60 81.27 10.31 1.24 [137]
Oil palm EFB 35.71 65.57 21.97 5.67 [137]
Oil palm husk 34.28 61.31 31.91 6.99 [137]
Oil palm petioles 37.01 71.65 20.94 2.06 [137]
Oil palm shell 27.7 21.6 44 10.31 [138]
Pineapple leaf 32.16 63.2 18.68 6.55 [137]
Rice husk 44.14 82.42 42.58 2.48 [137]
Rice straw 36.26 74.45 34.73 5.28 [137]
Rubber tree 45.84 73.84 21.42 2.86 [137]
Bamboo 47 25 21 7 [139]
Newspaper 40-55 25-40 18-30 - [1]
Chinquapin 46 20 30 4 [139]
Japan cedar 35 24 33 8 [139]
Banana stem 37.92 71.15 12.25 3.66 [137]
Coastal Bermuda grass 25 35.7 6.4 - [140]
Switch grass 45 31.4 12 - [140]

medium as it increases their density. The higher rate of extraction and
disintegration of biomass is achieved by using high-density solvents
[22]. This is because the high-density medium infiltrates sufficiently in
the fragments of biomass. Pressure has minute or even negligible
influence on both liquid oil and gas yield [97–100] at supercritical
conditions. It is for this reason that the effect of pressure on the
properties of water or on solvent is negligible in supercritical region.
The pressure in the reactor can be raised; either by raising the
temperature directly or by adding fluids like nitrogen. The reaction
inside the reactor is affected by pressure according to Le Chatelier’s
principle. The direction to which the equilibrium shifts at higher
pressure; shifts from solid to liquid phase or vice versa are decided
according to this principle. At the same time, it is a fact that the shift is
towards the direction constituting a lesser number of moles. For
example in both decarboxylation and dehydration reactions are de-
pressed at higher pressure [32]. The effect of pressure in HTC greatly
influences the formation of hydrochar. High pressures lead to high
temperatures; the breaking of biomass composition occurs hastily and
final product obtained with high quality of hydrochar is obtained in
HTC process. Hence, the effect of increased pressure is the enhance-
ment in the role in the formation of hydrochar in HTC process.
3.5. Effect of catalyst
The use of small amounts of hydrolytic agents or catalysts con-
siderably enhances the hydrolysis level. Catalysts differ according to the
hydrolysis process employed. In general, acid catalysts are the most
effective for hydrolysis [101], whereas the basic catalysts hinder the
formation of char and support the formation of liquid oil. The use of
catalyst also causes reduction in NOx. This is because the catalytic
chemical reactions quickly convert NOx into nitrogen and water.
Karagoz et al. [102] studied the effect of RbOH and CsOH (basic
catalysts) on pine wood and observed that liquid product increased as
the solid was reduced. A similar effect was observed by using K2CO3
(base) on sawdust [103].
Standards for the selection of good catalyst demand that they
should be thermally stable, effective, cost effective and have high
selectivity towards the required yield [104]. A number of catalysts

1295
S. Nizamuddin et al.
Fig. 7. Different catalyst with their ability to perform reactions and their respective advantages and disadvantages [144]. (For interpretation of the references to color in this figure, the
reader is referred to the web version of this article.)
are considered by international scientists for higher conversion of
biomass to biofuels [89,103,105]. Examples include sodium hydroxide
(NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3),
potassium carbonate (K2CO3), propanol (C3H8O), ethanol (C2H6O),
citric acid. Fig. 7 gives a variety of catalyst (blue boxes) with their
ability to perform different reactions (yellow boxes) and main advan-
tages and drawbacks (green boxes). The traits of a catalyst bear dire
significance to the formation of hydrochar. Catalysts have influenced
effects that serve as a seed in the production of hydrochar during HTC
process although small amounts are deployed for the enhanced rate of
formation of hydrochar. Therefore, catalyst particle diffusion into the
biomass to helps to breakdown the lignin and cellulose compound to
form hydrochar during HTC process.
4. Critical discussion
Biomass is an attractive feed for biofuels production. A range of
fuels can be produced from biomass sources. These include gaseous
fuels including hydrogen, methane as well as liquid fuels such as
biodiesel, fischer tropsch diesel, vegetable oil and bio-alcohols (ethanol
and methanol), biosynthetic oil and biochar. Biofuels hold more
advantages than fossil fuels in various aspects: availability of resources,
reduced emission of GHGs that makes it an environmental-friendly
fuel, energy security, foreign exchange saving, rural development,
sustainability, and biodegradability. Till today, the process of solid
biofuel production using HTC has not reached optimum conditions for
high yield of biochar. Previous studies suggest that various operating
parameters influence the production of hydrochar using HTC process.
The amount of char produced during HTC process in separation
process technology has become a major concern for development. In
the treatment process of adsorption, char is used as a new absorbent to
replace activated carbon (AC). This is because the cost of production of
AC is higher in comparison to the hydrochar produced during HTC
process. Hydrochar is a solid product with high carbon content and
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Renewable and Sustainable Energy Reviews 73 (2017) 1289–1299
high energy density obtained from organic matters such as dung,
firewood, and agricultural wastes. It is considered to be an outstanding
contender solid fuel because of its low fiber structure and high heating
value which makes it equally comparable to coal. Further, the
elemental composition of HTC hydrochar is approximately equal to
that of lignite or sub-bituminous coal. It is extremely feasible for
degradation during land applications and has numerous promising
benefits related to land fertility [64]. There are two eminent processes
that produce char from different biomass sources; pyrolysis and HTC.
The difference between pyrolysis and HTC is that the pyrolysis deploys
dry biomass and it is not environment friendly due to the volatile
matters released whereas the HTC process on the contrary is environ-
ment-friendly. In HTC, water is used as a solvent. Further, HTC has a
sum of further practical benefits also. In HTC, complex drying and
expensive separation process are theoretically saved because in HTC
the need for special drying of feed is eliminated. It is also easy to
separate solid product through filtration from the mixture. Char has
great mechanical strength, sufficient pore size distribution, and higher
pore surface area making it useful to serve as a fuel or chemicals. It can
be used as an absorbent for separation and purification, catalyst
support, solvent recovery and automobile exhaust emission control
[106]. Biomass with higher moisture content produces a greater
amount of char [25]. Char has many applications: it may be used as
a fuel in boilers in the form of briquettes, mixed with other biomass like
sugar cane baggasse, for the production of activated carbon, carbon
nanotubes and further, can be processed as well to form hydrogen-rich
gas [107]. Furthermore, HTC produced carbonaceous materials has
applications in the field of catalysis, adsorption, and electrochemistry
[108–110]. Hydrochar has a lower specific area which may be
improved either by thermal pretreatment or by removing extractable
to make it comparable to conventional charcoal [95,96]. A coal similar
to solid fuel with higher energy and higher carbon content can be
produced from biomass with low heating value and high moisture
content through HTC process. The effect of process parameters has
S. Nizamuddin et al.
great influence in the formation of hydrochar during HTC process.
Tuning of each and every single process parameter to achieve high
yield, high purity, well organized structure and well developed pore size
and high BET surface area is achieved once the process parameters
have been optimized. Hence, high yield of hydrochar produced using
HTC process is expected to create a major breakthrough in the near
future.
5. Conclusions
This paper provides detailed information guiding in detail towards
the synthesis of char using HTC process. Dehydration, decarboxylation,
aromatization, hydrolysis and condensation polymerization reactions
take place during HTC process. These reactions do not represent
consecutive reaction steps but rather form a parallel network of
different reaction paths. The presence of water accelerates the carbo-
nization process of biomass and affects the product distribution as well.
Simultaneously, water in biomass serves not only as a reacting medium
but also as a reactant.
Temperature is found to be the most influential factor in the HTC
process followed by residence time with feed type material being
positioned third. Higher temperatures produce a lower solid product,
whereas lower temperatures produce solids at a higher rate.
Temperature affects the physical and chemical characteristics of the
solid fuel produced; at a higher temperature, the carbon content is
higher whereas hydrogen and oxygen content is lower. This results in a
greater HHV value of biochar. The effect of feed material on HTC is
observed by the structure of biomass; biomass with higher content of
cellulose or hemicellulose will produce less solid fuel, whereas the
biomass with higher lignin content will produce more solid fuel. The
reaction time defines the product composition as well as overall
biomass conversion. For HTC reactions, the residence time is reported
to vary from several minutes to a few days. It is reported that longer
residence time supports gaseous and solid product formation, in
contrast to liquid product formation. Pressure has a positive effect on
the density of solvent or medium as an increase of pressure leads to an
increase in density. This is why the higher rate of extraction and
disintegration of biomass is achieved using high-density solvents. The
use of small amounts of hydrolytic agents or catalysts considerably
enhances the hydrolysis level. Standards set for selection of a good
catalyst that gives optimum performance include thermal stability,
effectiveness, cost effectiveness and high selectivity towards required
yield.
Acknowledgments
This work was supported by university of Malaya for fully funding
under HIR-MOHE Account no. D-000030-16001.
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