Sustainable Energy and Fuels From Biomass

Sustainable
Energy & Fuels

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REVIEW View Journal
Sustainable energy and fuels from biomass:

Cite this: DOI: 10.1039/d0se00784f
a review focusing on hydrothermal biomass
Published on 05 August 2020. Downloaded by Carleton University on 8/5/2020 6:36:08 PM.
processing
Koray Alper,a Kubilay Tekin, b
Selhan Karagöz a
and Arthur J. Ragauskas *cde
Fossil fuels are being replaced with renewable energy resources (biomass and biomass waste, solar,
geothermal, wind, etc.) to ensure sustainable development, reduce the dependence on fossil fuels,
address environmental challenges including climate change. Today, biomass produces 5 1019 kJ of
energy/year, which corresponds to 10% of the annual global energy consumption. Considering the
variety of biomass resources, this value is predicted to reach 150 1019 kJ by 2050. Biomass may
become even more important for use as an energy resource and chemical raw material in the 21st
century. Hydrothermal biomass conversion stands out as a promising and alternative technology.
Methods such as traditional gasification and pyrolysis require dry biomass. Hydrothermal techniques
have been developed to eliminate the cost and time required for drying biomass. The purpose of this
Received 22nd May 2020
Accepted 24th July 2020
process is to decompose biomass with a high moisture content into small molecules and reduce its
oxygen content to obtain liquid fuels or valuable chemicals. This review presents the current and future
DOI: 10.1039/d0se00784f
state of energy, energy sources, biomass properties and biomass conversion technologies with a focus
rsc.li/sustainable-energy on hydrothermal technologies.
domestic product (GDP). According to the Energy Information

1. Introduction Administration (EIA), although the world's total energy
The energy requirement of society constantly increases due to consumption was 282.817 quadrillion Btu in 1980, the annual
advancing technologies, growing population and the gross total energy consumption exceeded 500 quadrillion Btu in the
a
Department of Chemistry, Karabük University, 78050 Karabük, Turkey d
Joint Institute of Biological Science, Biosciences Division, Oak Ridge National
b
Department of Environmental Engineering, Karabük University, 78050 Karabük, Laboratory, Oak Ridge, TN 37831, USA
Turkey e
Center for Renewable Carbon, Department of Forestry, Wildlife, and Fisheries,
c
Department of Chemical and Biomolecular Engineering, University of Tennessee, University of Tennessee Institute of Agriculture, Knoxville, TN 37996, USA
Knoxville, TN 37996, USA. E-mail: aragausk@utk.edu
Dr Koray Alper got his bachelor's Dr Kubilay Tekin received his

degree in Chemistry at Selçuk PhD in Chemistry from Hacet-
University, Konya, Turkey, and tepe University, Turkey, and is
received his PhD in Chemistry at now working as an Associate
the Karabuk University, Turkey, Professor in the Department of
in 2019. He worked on hydro- Environmental Engineering at
thermal biomass gasication at Karabuk University, Turkey. His
the Tokyo Institute of Tech- research focuses on the produc-
nology, Japan. He is now tion of valuable chemicals and
working as a lecturer at the materials from renewable sour-
Bulent Ecevit University, Zon- ces and the removal of heavy
guldak, Turkey. He has been metal ions from aqueous solu-
working on thermochemical tions. He has extensive experi-
processing of biomass since ence of academic research at Hacettepe University, Karabuk
2015. University, Queen Mary University of London, UK, and RMIT
University, Australia.
This journal is © The Royal Society of Chemistry 2020 Sustainable Energy Fuels
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Sustainable Energy & Fuels Review
2010s.1 The world's energy consumption is predicted to reach taken millions of years to form, biomass forms in years or even
815 quadrillion Btu in 2040, representing an increase of 48%.2 months.18
Today, this energy demand is largely met by fossil fuels, which Since the CO2 released due to biomass use has previously
are nite and have serious negative effects. If we continue to been used to grow plants through photosynthesis, unlike fossil
accelerate the use of fossil fuels, greenhouse gases effects will fuels, biomass energy is regarded as carbon neutral.11,18,19 For
increase, and contribute to global warming.3 The greenhouse this reason, biomass is a promising alternative that can replace
effect is caused by gases such as carbon dioxide (CO2), methane fossil fuels, which are nite and have detrimental effect on the
(CH4), nitrogen oxide (N2O), and water vapor (H2O).4 While the environment.20 Biomass is produced from CO2 and water (H2O)
average atmospheric CO2 concentration was approximately using sunlight as the energy resource, while oxygen (O2) is
285 ppm for about 400 000 years before the industrial revolu- released as a byproduct.21
tion, the average atmospheric CO2 concentration reached The use of biomass energy may provide several benets:
376 ppm as of 2005 and is still increasing.5 By the end of the Decreased greenhouse gas emissions and, therefore,
century, the CO2 concentration is predicted to double that of the a cleaner environment;
preindustrial revolution, which may cause the average global Decreased foreign-source dependence as a result of
temperature to increase from 1.5 to 4.5 C.5 If the increasing use replacing imported fossil fuels with biomass;
of fossil reserves does halt by 2050 the average global temper- Development of economical opportunities in rural areas;
ature increase will exceed the critical level of 2 C.6 Nonrenew- and
able fossil fuels must be replaced with renewable energy Decreased waste disposal issues.15
resources (biomass and biomass waste, solar, geothermal, Despite its advantages, biomass has a low energy density (an
wind, etc.) to facilitate sustainable development, rural devel- upper heating value of 15–20 MJ kg1) and needs to be con-
opment, and address environmental challenges.7–12 This verted into valuable products, which can be achieved using
process of replacement must begin as soon as possible since it various methods.22 However, it is not an easy task to efficiently
will require a considerable amount of time.13 Among the alter- convert lignocellulosic biomass into valuable products because
native energy resources, lignocellulosic biomass, which is lignocellulosic biomass is heterogeneous and has a structure
renewable and whose supply is abundant, is a promising that is difficult to decompose.14 Thus, various conversion tech-
resource for the sustainable production of valuable chemicals nologies are used to produce biomass-based fuels, organic
and fuels, which are largely obtained from oil as of today.14 chemicals, polymers, and materials.12 These conversion tech-
Presently, biomass produces 5 1019 kJ of energy, which nologies can be divided into two main groups, thermochemical
corresponds to 10% of the annual global energy consumption. and biochemical technologies. Thermochemical conversion is
Considering the variety of biomass resources, this value is performed by subjecting biomass to a thermal treatment.
predicted to reach 150 1019 kJ by 2050.15 Biomass may become Thermochemical technologies include combustion, gasica-
even more important for use as an energy resource and as tion, pyrolysis, and liquefaction.23 Hydrothermal liquefaction
a chemical raw material in the 21st century.16 It is asserted that (HTL) is an effective technique used to convert biomass into
drugs, agricultural chemicals, plastics, and fuels, which are a liquid fuel resource.22 Various catalysts are used in these
obtained from fossil fuel-based raw materials, will be produced technologies to reduce the production costs and increase the
using renewable biomass.17 Additionally, while fossil fuels have
Dr Selhan Karagöz was born in Dr Arthur J. Ragauskas held the

Eskişehir and raised in Izmir, rst Fulbright chair in Alterna-
Turkey. Dr Karagöz obtained his tive Energy and is a Fellow of
PhD at the Ege University, AAAS, IAWS and TAPPI. In 2014,
Turkey in 2002 and then moved he assumed a Governor's Chair
to a postdoctoral position at the for Biorening based in the
Okayama University, Japan University of Tennessee's
where he conducted research on Department of Chemical and
hydrothermal biomass process- Biomolecular Engineering, with
ing. He worked as a visiting a complementary appointment
scientist at the Penn State in the UT Institute of Agriculture
University, USA, Malaysia and serves in the US Energy and
University of Technology, Environmental Science Direc-
Malaysia, Nagoya Institute of Technology, Japan and Tallinn torate, Biosciences Division, and ORNL. His research program is
University of Technology, Estonia. He is currently working as a full directed at understanding and exploiting innovative sustainable
Professor at the Department of Chemistry of Karabuk University, bioresources. He is the recipient of the TAPPI Gunnar Nicholson
Turkey. Gold Medal Award, the ACS Affordable Green Chemistry award
and AIChE Green Processing Award.
Sustainable Energy Fuels This journal is © The Royal Society of Chemistry 2020
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Review Sustainable Energy & Fuels
yields and selectivity.24–26 This study provides a comprehensive

overview of the hydrothermal processing of biomass.
2. Energy
Energy is the foundation of modern society. In classical
physics, energy is dened as the ability to do work.27,28 Energy
use is directly or indirectly related to the development of
humanity.29 In the past, fossil fuels had been consumed rapidly
Fig. 2 Distribution of renewable resources by year.
for energy, and their negative impacts on the environment were
largely ignored.30 Although conventional energy resources

based on oil, coal, and natural gas are signicant contributors
to economic development, they are growing concerns regarding
their environment and human health impacts.31 According to
the 2016 report released by the World Energy Council (WEC),
signicant changes had been initiated by the use of energy
resources over the previous 15 years.32 As shown in Fig. 1, in
2008, oil, natural gas, and coal accounted for 35.4%, 22.0%,
and 29.9% of the world's energy consumption, respectively,
while renewable resources accounted for 7.4% of the world's
energy consumption. In 2018, oil, natural gas, and coal
Fig. 3 Distribution of nonrenewable resources by year.
accounted for 33.6%, 23.9%, and 27.2% of the world's energy
consumption, respectively, while renewable resources accoun-
ted for 10.9%.33
As shown in Fig. 2, the world extracted 36.037 quadrillion basic needs of humanity can be divided into two groups:
kilojoules from renewable resources in 2008, and this value primary and secondary resources. Primary energy resources
reached 63.212 quadrillion kilojoules in 2018, representing an include both renewable and nonrenewable energy resources.
increase of approximately 75%. However, as shown in Fig. 3, Secondary energy resources, on the other hand, are obtained
nonrenewable resources reached 517.155 quadrillion kilo- from the conversion of primary energy resources.
joules, an increase of 15%, within the same period.33 These data 2.1.1. Primary energy resources. Energy can be gathered
indicate that there are substantial opportunities to further directly from the environment. Primary energy resources
develop renewable energy resources. include both nonrenewable (oil, natural gas, coal, and nuclear)
and renewable energy resources (hydro energy, biomass, solar,
wind, and geothermal).28
2.1. Energy resources 2.1.1.1. Nonrenewable energy resources. Fossil fuels (coal, oil,
The main energy resource of the world is the sun.27 Almost all and natural gas) and nuclear energy are considered to be
energy resources available on our planet, such as water, wind, nonrenewable energy resources. Although fossil fuels, which
fossil fuels, and biomass, are derived directly or indirectly from constitute the majority of nonrenewable energy resources, can
the sun.34 As shown in Fig. 4, the energy resources that meet the detrimentally impact the environment, they guide modern
technology and represent a billion dollar industry, which
substantially impacts the global economy.35 Fossil fuels have
formed over millions of years by decomposing the remains of
plants and animals under heat and pressure.28,35
Oil consists of hydrocarbons (paraffin, naphthalene, and
aromatics), oxygen, nitrogen, sulfur, and trace amounts of
metallic components.36 The content of oil samples around the
world is 82–87% carbon and 11–15% hydrogen, and the
remaining components are oxygen, nitrogen, and sulfur. The
oxygen and nitrogen contents rarely exceed 1.5%, while the
sulfur content may be as high as 6% in exceptional cases.37
Eighty-four percent of oil is converted to rich energy fuels such
as gasoline, diesel, jet fuel, and liqueed petroleum gas (LPG),
and the remaining oil is converted to lubricants, medicines,
fertilizers, chemicals, and plastics.28
Natural gas is a type of fossil fuel consisting of various types
of gases and has a combustion enthalpy per unit mass higher
Fig. 1 Distribution of the world's energy resources in percentages. than that of gasoline or diesel and very similar properties to
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Fig. 4 Primary and secondary energy resources.
Table 1 Typical natural gas composition39 the atmosphere and hydrolyzed to sulfuric and nitric acid
causing acid rain if not captured.42,43
Gas Content (%)
Although nuclear energy can be harnessed by two methods,
Methane 92.041 ssion and fusion, an effective fusion system remains
Ethane 3.241 a research challenge for power plants.44 Available reactors are
Propane 0.654 based on the ssion system and process either uranium or
Butane 0.016 thorium. The energy derived from ssion reactions is used as
Pentane 0.099
thermal energy and transferred to a liquid (water, gas, liquid,
Nitrogen 3.008
Carbon dioxide 0.587 metal, or molten salt) to generate steam. Steam is then sent to
turbines to generate electrical energy.45 As of February 12, 2019,
there are 452 nuclear power plants in 30 countries around the
methane, its main component.38 As shown in Table 1, the world, generating 398 667 MWe of energy, and 55 nuclear power
majority of natural gas consists of methane.39 Natural gas is plants are under construction in 18 countries, with a capacity of
usually found in reserves, dissolved in oil under high pressures 56 643 MWe. The Akkuyu Nuclear Power Plant in Turkey, which
or accumulated on oil.35 has a capacity of 1114 MWe, is one of these power plants under
Coal is a brown or black, brittle, combustible organic sedi- construction.46 Table 3 shows the pros and cons of nonrenew-
mentary rock formed by the decomposition of vegetation under able energy resources.47
high temperatures and pressures and contains varying amounts 2.1.1.2. Renewable energy resources. The need to conserve
of carbon, hydrogen, nitrogen, oxygen, and sulfur.40 Coal is energy and nd alternative energy resources has increased due
classied as anthracite, bituminous coal, sub-bituminous coal, to the high demand for energy around the world, concerns
and lignite depending on its heating value and carbon content related to global climate change, and the expectation that fossil
(Table 2).41 Coal produces more CO2 than other fossil fuels, such fuels will become less available and more costly in the next
as crude oil, due to its high carbon content, and therefore, it has century.48,49 Biomass, wind, geothermal, solar, and water energy
a signicant effect on global warming.28 Also, coal combustion resources stand out as renewable energy resources.50 The
gases, sulfur dioxide and nitrogen oxides, my be released into potential of these resources is quite high, and these resources
have the capacity to meet the world's energy requirement many
times over.31,51 In addition to the signicant decline in the costs
of systems based on solar and wind energy during the last 30
Table 2 Heating values and carbon contents of the different coal years, uncertainties regarding oil and natural gas prices are
types41 accelerating the shi to renewable energy. Additionally,
economic and societal support for these renewable energy
Carbon content
systems are rapidly advancing.31 The pros and cons of renew-
Heating value (Btu kg1) (wt%)
able energy resources are shown in Table 4.47
Anthracite 29 762–34 392 86–98 Water, which moves due to the effect of gravity, contains
Bituminous coal 18 298–34 392 46–86 energy by nature. When generating electrical energy, the work
Subbituminous coal 18 078–24 692 42–52 done by water is usually measured in units of kilowatt hour (kW
Lignite 12 125–18 298 46–60
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Table 3 Pros and cons of nonrenewable energy resources47
Oil Pros Plentiful supply Readily transported Many uses Source of revenue
for exporters
Cons Majority of supply is Risk of rapid depletion Rising costs Source of dependence Source of greenhouse
removed from major markets and insecurity gas emissions
for importers
Natural Pros Plentiful supply Readily transported Many uses Source of revenue for
gas exporters
Cons Signicant supply is Rising costs Source of greenhouse Source of dependence
removed from major markets gas emissions and insecurity
for importers
Coal Pros Plentiful and supplier diversity Inexpensive Many uses Easily stored Source of revenue for
exporters
Cons Risk of rapid depletion Mercury, CO2, and other Threat fora Processing waste ash Source of insecurity
emissions climate change remains a challenge for importers
Nuclear Pros Low operating costs Low-carbon pathway Scientic benets
to cheap energy
Cons Requires high level Prone to cost overruns Presents major Waste and safety Has troubling links with
of expertise and long lead times health risks challenges weapons proliferation
a
Driver for carbon capture technologies.
h). Water has two types of energy, potential energy caused by its produce 4 times the total energy capacity of the world, approx-
location and kinetic energy due to its motion. Water energy is imately 3000 GW.53 In 2012, 103 trillion kW h of electrical
converted to electrical energy using a main carrier that is known energy was generated from solar energy worldwide, while this is
as a water wheel or hydraulic turbine.52 The electrical energy estimated to reach 962 trillion kW h by 2040.2
derived from water was 2100 terawatt hours in 1997, 3000 Wind energy is generated by turbines connected to grid
terawatt hours in the early 2000s and may reach 6000 terawatt networks, which convert wind power into electricity. The most
hours by 2050.51 According to the EIA, 3645 trillion kW h of common wind turbines generate an electrical energy of 10 kW
electrical energy was generated from water energy worldwide in or less, while there are also turbines that generate an electrical
2012, and this is estimated to reach 5571 trillion kW h by 2040.2 energy of 1.5 to 5 MW.54 In 2012, 520 trillion kW h of electrical
Although the impact of water storage devices on the environ- energy was generated from wind energy worldwide, while this is
mental remains a societal issue. estimated to reach 2452 trillion kW h by 2040.2
Solar energy is the most abundant of all renewable energy Geothermal energy is the heat derived from volcanic activi-
resources. The sun emits an energy of 3.8 1023 kW, and ties, the radioactive decay of minerals, the formation of the
approximately 60% (1.8 1014 kW) of earth's solar energy rea- planet, and the solar energy absorbed on the surface.28 Although
ches the surface. The remaining energy is reected into space or the geothermal energy potential is approximately 140 000 000
absorbed by the atmosphere. Converting 0.1% of the energy 1018 J, even its reachable reserve (approximately 434 1018 J)
reaching the surface with a yield of 10% will make it possible to exceeds the annual primary energy consumption.55 Geothermal
Table 4 Pros and cons of renewable energy resources47
Hydroelectric Pros Domestic resource Inexpensive Clean source of Easy to manage once
energy established
Cons Causes environmental Affected by drought, May entail the forced Decommissioning can
damage technical failures, and relocation of communities represent hidden costs
terrorist attacks
Solar and Pros Domestic resource Easy to scale-up, Clean source of energy Can minimize impacts of
wind decentralized fossil fuel price increases
Cons Intermittency poses Can be undermined by Costs may rise
hidden costs environmental or climatic
changes
Biofuels Pros Most nations have Variety of sources A good use of waste Enhances agricultural Can minimize oil
some supply development imports
Cons Not enough to fully Requires continued Gives rise to
replace other fuels expansion of land-use deforestation
to expand supply and the resulting
environmental
insecurity
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energy has great potential in terms of energy generation and element of biomass.23,61 Nitrogen (N) returns to soil as fertilizer
domestic heating. However, geothermal energy contributes to and enhances plant growth and yield. Sulfur (S) is found in
a small portion of the world's primary energy consumption, and amino acids, proteins, and enzymes and is an important
the electricity generated by geothermal energy accounts for less nutrient for plant growth. Oxygen (O) is released during
than 1% of the world's electricity generation.32 There are four photosynthesis and is a vital element in the composition of
types of geothermal energy: hot water or steam at a depth of biomass.23
100–4500 meters, hot water that contains methane dissolved at Biomass, which has always been an important energy
high pressures and exists at a depth of 3–6 kilometers, geolog- resource for humankind, produces 50 1018 J of energy
ical structures at abnormal temperatures with little to no water, currently, corresponding to 10% of the world's energy
and molten rock (magma) at temperatures of 700–1200 C.55 In consumption.15,56 In addition to being a renewable carbon
2012, 68 trillion kW h of electrical energy was generated from resource for energy, fuel, and chemicals, biomass has allowed
geothermal energy worldwide, while this is estimated to reach for less dependence on oil and reduced greenhouse gas emis-
395 trillion kW h by 2040.2 sions.62 Biomass (such as that derived from herbal, herbaceous,
ligneous, and organic wastes) possesses a great advantage over
fossil fuels, which is formed over thousands or millions of
3. Biomass years.63 As shown in Fig. 6, the use of fossil fuels causes the
release of CO2, which was stored millions of years ago, meaning
Biomass contains organic substances that include all plant
additional CO2 is released to the atmosphere; however, since
species that live or have recently existed on the planet and their
the CO2 released as a result of biomass use is taken from the
waste, in which solar energy is stored as chemical bonds.18,56,57
atmosphere during plant growth, additional CO2 release does
Biomass is a sustainable and renewable resource and is
not occur, and thus, there are no net greenhouse gas
constantly formed, as shown in Fig. 5, via photosynthesis using
effects.19,56,58,59,63–65
solar energy, CO2 in the atmosphere and H2O in the
Biomass can be converted to electrical energy, thermal
soil.21,26,56,58,59 Annually, 170 billion tons of biomass, 75% of
energy, vehicle fuels, and valuable chemicals.56,66 Biomass is
which is classied as carbon, is produced by nature via
quite attractive for biofuel production due to following reasons:
photosynthesis.21
Biomass is a renewable resource;
Biomass is also known as a heterogeneous mixture formed
Biomass is an important raw material for valuable chem-
by organic substances and a small amount of inorganic
icals and polymers;
substances. A typical dry biomass contains 30–40% oxygen, 30–
Biomass is environmentally friendly due to carbon
60% carbon, and 5–6% hydrogen by weight, while nitrogen,
neutrality; and
sulfur, and chlorine account for approximately 1% of the
Biomass has economic potential due to the unreliability of
biomass together with other inorganic elements.60 Carbon (C)
oil prices.50,65
comes from atmospheric CO2 during photosynthesis and is the
Biomass resources contain less carbon and hydrogen and
element that makes the greatest contribution to the total heat-
have a higher oxygen content than oil.67 The H/C and O/
ing value of biomass.23 Hydrogen (H) integrated into the
C atomic ratios indicate the heating value of a fuel. To convert
chemical structures of carbon and phenolic polymers, turns
biomass into liquid products, which can replace oil, the oxygen
into water (H2O) during combustion and is another important
Fig. 5 Regrowth of biomass via photosynthesis. Fig. 6 CO2 cycle of fossil- and biomass-based fuels.
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in the biomass structure must be removed in the form of H2O, a structure that supports intramolecular and intermolecular
CO and CO2, the O/C ratio must be reduced, and the H/C ratio hydrogen bonds.79 Additionally, the hydrogen and van der
must be increased.8,59,68 However, the high O/C atomic ratio in Waals bonds in the cellulose structure impart cellulose with
cellulosic biomass becomes an advantage in terms of extracting a high strength and high resistance against biological attacks.
valuable chemicals, which cannot be obtained inexpensively Cellulose is not water soluble due to its crystal structure and is
from raw fossil fuel materials.69–71 resistant to hydrolysis.12 Cellulose is a very important resource
Biomass can be converted into gas fuels, such as hydrogen for paper and cardboard production. Additionally, cellulose
and methane; liquid fuels, such as biodiesel; Fischer–Tropsch derivatives are used in pavements, laminates, optical lms,
diesel, vegetable oil, ethanol, and methanol; and solid fuels, pharmaceuticals, foods, and textiles.80 Fig. 8 shows the struc-
such as biochar and hydrocarbons.65 ture of cellulose.
3.1.2. Hemicellulose. Hemicellulose, the second most

3.1. Chemical structure of lignocellulosic biomass important component of lignocellulosic biomass, is also
known as polyose.81 Hemicellulose is a heteropolysaccharide
Lignocellulosic biomass consists of cellulose (40–50 wt%),
with typically b-1,4-linked sugar units.82 Hemicellulose has
hemicellulose (15–30 wt%), lignin (16–33 wt%) and extractive
a heterogeneous structure and consists of uronic acid, hexoses,
materials (1–10 wt%).72 Fig. 7 shows the chemical structure of
and pentoses.83 Hemicellulose contains various mono-
biomass.
saccharides, such as D-xylose, L-arabinose, D-glucose, D-galac-
3.1.1. Cellulose. Cellulose, the most abundant component
tose, D-mannose, D-glucuronic acid, 4-O-methyl-D-glucuronic
of biomass, is considered as a near innite resource of chem-
acid, and D-galacturonic acid.74,81 Hemicellulose exhibits
icals and fuels.73 Cellulose is found in plant cell walls and
a lower polymerization degree than cellulose, is largely soluble
constitutes approximately one-third of all plant material.74,75
in alkali media and is easily hydrolyzed.83 While hemicellulose
The French chemist Anselme Payen describes cellulose as
is amorphous and hydrophilic, it serves as an interbrous
a resistant brous solid that remains aer the treatment of
connective material that provides support to cellulose micro-
various plant tissues with acid and ammonia and extraction
brils.84 In addition, hemicellulose is known to form covalent
with water, alcohol, and ether.76 Cellulose is composed of linear
bonds with the functional groups found in lignin and interacts
polymers, in which glucose units bond to each other by b-1,4
with cellulose via hydrogen bonds.75 Fig. 9 shows the building
glycosidic ester bonds.56,58,77,78 The average molecular weight of
blocks of hemicellulose.
native cellulose is 100 000.50,56 Cellulose chains possess
Fig. 7 Representative chemical structure of biomass (note: lignin image from https://public.ornl.gov/site/gallery/originals/
Contemporary_View_of_L.jpg).
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Fig. 8 Structure of cellulose.
3.1.3. Lignin. Lignin is the most common aromatic poly- phenylpropane units.85 Lignin constitutes 16–33% of wood.86
mer besides cellulose in plants.75 Lignin is a term that was Lignin has a relatively high molecular weight, which is difficult
introduced by Candolle in 1819 and is derived from the Latin to measure.85 Lignins are complex polymers that form by the
word for wood (Lignum).74 Lignin is a complex polymer with dehydrogenation of p-coumaryl, sinapyl, and coniferyl.87 Fig. 10
a three-dimensional amorphous structure consisting of shows the structures of lignin monomers. Sowood lignin
Fig. 9 Building blocks of hemicellulose.
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consists of coniferyl alcohol and a small amount of coumaryl Tannins are dened as polyphenolic carboxylic acids
alcohol. Hardwood lignin consists of both coniferyl and sinapyl frequently esteried to sugar, usually, glucose. They are further
alcohols and a small amount of coumaryl alcohol. Herbaceous divided into two subgroups, hydrolysable tannins and condensed
plant lignin consists of phenylpropane (p-coumaryl, sinapyl, tannins.92 The ester linkages of tannins can be readily hydrolyzed
and coniferyl alcohols) units and p-hydroxycinnamic acids (p- by acids, bases, or enzymes. Terpenes are hydrocarbons that bear
coumaric acid, ferulic acid, and sinapinic acid).88 the same isoprene unit and one or more carbon–carbon bonds;
Compared to polysaccharides, lignin is more resistant to natural and synthetic derivatives of terpenes containing oxygen
microbial decay due to its complex structure and diverse are referred to as terpenoids.21,93 Terpenoids are found in essential
bonds.89,90 However, when efficiently depolymerized, lignin is oils and are components of resins, steroids, and rubber. Readily
an important resource of valuable chemicals, fuels, and fuel available and inexpensive terpenoid types, such as pinene and
additives.20 limonene, are ideal starting compounds for the synthesis of some
3.1.4. Extractive substances. The term ‘extractive important chemicals.21 Stilbenes are 1,2 diphenylethylene units
substances’ is used to refer to a wide variety of compounds that and contain conjugated double bonds. The pinosylvin found in
can be extracted by using polar and/or nonpolar solvents.75 pine trees can is one example.74
These extracts are usually compounds with low molecular
weights.91 Extractive substances, such as fats, free fatty acids,
waxes, resins, tannins, gums, terpenoids, avonoids, stilbenes, 4. Biomass conversion technologies
tropolones, and volatile hydrocarbons, usually amount to only
Biomass conversion technologies are divided into two groups,
a small portion by weight of wood.37 Each extractive substance
biochemical and thermochemical technologies. Each one has
has a different task, which allows a tree and other bioresources
its own advantages and disadvantages.94,95
to maintain its biological functions. For example, fats are the
energy providers of wood cells, while terpenoids, resins, and
phenolic substances protect wood against microbial and insect 4.1. Biochemical conversion technologies
attacks.74 Fig. 11 shows the composition of extractive The biochemical conversion of biomass involves the use of
substances, such as stilbenes, terpenes, and avonoids. bacteria, microorganisms, and enzymes to convert biomass into
a gas (i.e., biogas) or liquid (i.e., bioethanol) fuel.96 This process
Fig. 10 Lignin monomer compositions.
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Fig. 11 The compositions of stilbenes, terpenes, and flavonoids.
is substantially slower than the thermochemical process and reduce the recalcitrance biomass, followed by hydrolyase
does not require signicant energy.59 Biochemical conversion enzymes releasing sugars from polysaccharides and the sugar
involves two processes: fermentation (ethanol or other low MW are then converted into ethanol or other chemicals with the
alcohols production) or digestion (biogas production).97 During help of yeasts or other microbial agents.59 There are now many
anaerobic digestion, bacteria receive oxygen from the biomass examples of fermenting lignin to lipids or PHA. Challenges
and generate methane and carbon dioxide as well as solid associated with biochemical conversion reside about the overall
products. During aerobic digestion, microorganisms receive cost factors especially the pretreatment stage and the cost
oxygen from the air and release carbon dioxide, heat, and solid cellulases in today's low-cost fuel scenario.98
products. Prior fermentation, a pretreatment is typically used to
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4.2. Thermochemical conversion technologies liquid fuels.105,106 For a successful gasication process, the raw
material properties (moisture, ash, and volatiles) and pretreat-
Thermochemical conversion technologies allow fuel, chem-
ment method (drying, particle size, fractionation, and leaching)
icals, or electricity to be obtained from biomass using heat and
are very important.107 The biomass gasication process steps
catalysts. The thermochemical process is performed at high
may involve drying, thermal decomposition or pyrolysis, partial
temperatures (at least a few hundred centigrade and sometimes
combustion (of some gases, vapor, and coal), and the gasica-
over 1000 C) with or without a catalyst.95 Four techniques are
tion of decomposed products.59
used for the process: burning, pyrolysis, gasication, and
hydrothermal techniques. 4.2.4. Hydrothermal techniques. Hydrothermal techniques
4.2.1. Burning. Burning is the oldest biomass conversion are dened as chemical and physical conversion techniques
performed at high temperatures (200–600 C) and high pres-
process used to obtain energy.59,99 Until the early 1900s, burning
sures (5–40 MPa) in liquid or supercritical water.108 Water is

was used for various purposes, such as heating, chemical and
indispensable for life and is a signicant component of plant
coal production, and mechanical and electrical energy genera-
biomass; water accounts for 10–60% of lignocellulosic biomass
tion. The burning process takes place as a result of the chemical
and even higher ratios for microalgae.109
reaction occurring between biomass and oxygen, and the main
Water acts as the reactant, solvent, and catalyst in hydro-
products of the process are carbon dioxide and water.59,95,99,100
The ame temperature may exceed 1650 C depending on the thermal techniques.110 Many organic nonpolar compounds
heating value and moisture content of the fuel, the amount of become water miscible under hydrothermal conditions.95 In
addition, water acts as an acidic and basic catalyst in reaction
air used to burn the fuel, and the structure of the furnace.95 A
environments due to the H3O+ and OH ions that it
low moisture content is desirable during the burning process.100
contains.95,111,112 Another catalytic function of water is its ability
4.2.2. Pyrolysis. Pyrolysis is the process of converting
to participate in certain reactions at the transition states.95 As
biomass into liquid, solid, or gas products by thermal decom-
the temperature increases, the hydrogen bonds between water
position in the absence of oxygen.59,101 Gases and bio-oils come
molecules weaken, the dielectric constant decreases, and water
from the volatile fraction of biomass, while the solid product,
called char, comes mostly from the stable carbon component.100 behaves as a nonpolar solvent as a result.112
Bio-oils are dark brown organic liquids containing high Methods such as traditional gasication and pyrolysis
require dry biomass.109 Hydrothermal techniques have been
amounts of oxygenated compounds.102 This mixture, containing
developed to eliminate the cost and time required to dry
components such as acids, esters, alcohols, ketones, aldehydes,
biomass.109,113 Valuable plant chemicals, such as resins, oils,
sugars, furans, and phenol, is obtained by depolymerizing and
phenolic compounds, and phytosterols, are extracted during
decomposing cellulose, hemicellulose, and lignin.7 The result-
the hydrothermal process at approximately 100 C. At 200 C
ing products present with differences depending on the pyrol-
and under a 2 MPa pressure, the biomass is subjected to
ysis method and reaction parameters.101 Water is undesirable in
raw materials and pyrolysis oils; the presence of water is decomposition to obtain cellulose and hemicellulose decom-
complicated due to the stability, viscosity, pH, abrasiveness, position products, such as furfural or 5-hydroxymethylfurfural.
A bio-oil (i.e., biofuel precursor, a nonaqueous soluble organic
and other properties.103 The higher the water content is, the
phase) is obtained at 300–350 C and under 12–18 MPa of
lower the net energy obtained from the pyrolysis oil.104 Table 5
pressure. Finally, a gas product containing a signicant amount
summarizes the pyrolysis techniques.
of methane is formed at 600–650 C and under 30 MPa pres-
4.2.3. Gasication. Gasication is the process of converting
sure.95 In addition to subcritical and supercritical water,
carbonaceous materials into a combustible or synthetic gas by
hydrogen-donating solvents, such as alcohol, decalin, and tet-
reacting the material with air, oxygen, vapor, carbon dioxide, or
a mixture of these gases at a temperature of 760 C or higher.105 ralin, may be used for biomass conversion.114 Hydrothermal
Gasication produces gases such as H2, CO, H2O, CO2, and CH4, techniques are classied as carbonization, gasication, and
liquefaction. Table 6 shows the temperature ranges used by
which are used to generate electricity, heat, chemicals, and
hydrothermal techniques.
Table 5 Pyrolysis techniques101
Reaction time Heating Temperature ( C) Main product
Carbonization Hours-days Very slow 400 Biochar

Traditional 5–30 min Slow 600 Biochar, bio-oil, and gas
Fast 0.5–5 hours Quite fast 650 Bio-oil
Flash Liquid <1 hour Fast <650 Bio-oil
Gas <1 hour Fast <650 Chemicals and gas
Ultra <0–5 hours Very fast 1000 Chemicals and gas
Vacuum 2–30 hours Moderate 400 Bio-oil
Hydropyrolysis <10 hours Fast <500 Bio-oil and chemicals
Methanopyrolysis <10 hours Fast >700 Chemicals
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Table 6 Hydrothermal techniques and temperature ranges subcritical conditions; therefore, ionic reactions may be domi-
nant, whereas the free radical reactions necessary for gasica-
Technique Temperature ( C) Reference
tion are limited.127 The density of supercritical water can be
Hydrothermal 180–250 115 altered from high (as liquid) to low (as gas) without a phase
carbonization transition occurring by changing the pressure and temperature
Hydrothermal liquefaction 280–380 116 values.120 The density of water is lower under supercritical
Hydrothermal gasication 400–700 107 conditions, which means that the water ionization constant is
substantial lower, and ionic reactions are somewhat inhibited
due to the low dielectric constant, which supports the free
radical reactions necessary.127 The free radical reaction types are
4.2.4.1. Subcritical and supercritical water. Water is an
as follows: initiation, hydrogen transfer, radical isomerization,

inexpensive and environmentally friendly solvent; it is not radical addition, radical dehydratization, radical substitution,
combustible, explosive, or toxic which facilitates industrial and radical termination reactions.128 This decrease in the
processes.117 (Note: Given climate change patterns, access to density is associated with other properties, such as the resolving
abundant water resources has become a growing issue.) The power, degree of hydrogen bonds, polarity, dielectric constant,
interactions between water molecules are very strong due to its molecular diffusivity, and viscosity.121 Fig. 12 shows the behav-
strong hydrogen bonds, and water has a high critical point.118 iors of water and the temperature and pressure ranges used by
Table 7 shows the physical and chemical properties of water hydrothermal techniques.
under normal and subcritical/supercritical conditions.119 As shown in Table 8, while the dielectric constant of water is
Water reaches a critical point at 374.2 C and under 78.46 at 25 C and 0.1 MPa, it decreases to 14.07 at 350 C and
a 22.1 MPa pressure.112,120,121 Water close to its critical point 20 MPa, and it is possible to decrease the dielectric constant of
displays signicantly different thermophysical properties water to approximately 1 by modifying the temperature and
compared to water under normal conditions.122 Water close to pressure values.129 When water reaches the supercritical point,
its critical point acts as a solvent, reactant, and catalyst in the dielectric constant drops to approximately 6, and water
reaction environments.111 Water below its critical point is behaves as a nonaqueous solvent at this level.120 The dielectric
referred to as subcritical water, while water above its critical behavior of water is similar to methane at 200 C, acetone at
point is referred to as supercritical water.118 Below the critical 300 C, methylene chloride at 400 C, and hexane at
point, the vapor pressure curve separates the liquid from the gas 500 C.130
phase, and the properties of both phases become gradually In an unconventional reaction environment, supercritical
more similar as the critical point is approached, and nally, water displays a wide variety of conversions, including hydro-
become identical at the critical point.123 While water is not genation, carbon–carbon bond formation, dehydration, decar-
a suitable solvent for many organic compounds under standard boxylation, partial oxidation and hydrolysis, and the rate and
conditions (25 C and 0.1 MPa), it behaves as an apolar solvent selectivity of these reactions can be adjusted by selecting the
and provides a quite effective reaction environment for organic appropriate temperature, catalyst, and water density, which
compounds under supercritical conditions.121,124 The ionization allows the functional group conversion reactions to be
constant of water (Kw ¼ [H+][OH]) under room conditions is controlled.111
approximately 1014 but increases to approximately 1011 near 4.2.4.2. Hydrothermal carbonization. The thermochemical
the critical temperature.125 In this case, water provides an effi- conversion of the organic matter in biomass occurs in an
cient environment for organic reactions with both acidic and anaerobic environment in the presence of subcritical water
basic catalysts.126 The density and dielectric constant of water which is referred to as hydrothermal carbonization, and the
signicantly impacts the solubility of different compounds. For resulting solid product is called hydrothermal carbon (HTC) or
subcritical water, a low dielectric constant allows for a solution hydrochar.132 Hydrothermal carbonization is a process that
of organic compounds, whereas a high ionization constant reduces both the oxygen and hydrogen contents (dened as the
provides an acidic environment for hydrolysis reactions.118 O/C and H/C atomic ratios) by dehydration and decarboxylation
Water exhibits properties similar to those of liquids under
Table 7 The physical and chemical properties of water under normal and subcritical/supercritical conditions.119
Normal water Subcritical water Supercritical water
Temperature ( C) 0–100 100–374 >374

Vapor pressure (MPa) 0.003 (24 C) 22.1 (374 C) >22.1
Phase Liquid Liquid No phase differentiation
Density (r) [g cm3] 0.997 (25 C) 0.692 (330 C, 30 MPa) 0.252 (410 C, 30 MPa)
Viscosity (m) [Pa s] Liquid: 884 gas: 9.9 (25 C) Liquid: 50.4 gas: 30.7 (371 C) Low
Thermal capacity (Cp) [J g1 K1] Liquid: 4.2 gas: 2 (25 C) Liquid: 69 gas: 145 (371 C) 1300 (400 C, 25 MPa)
Dielectric constant (3) 78.5 (25 C, 0.1 MPa) 18.2 (330 C, 30 MPa) 5.9 (400 C, 25 MPa)
Ionization constant (Kw) [mol2 L2] 1014 (25 C) 1011 (300 C) 1020 (400 C)
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is usually performed within a temperature range of 400 and

700 C to obtain methane or hydrogen in high yields.95,108 The
gasication process can be performed under subcritical condi-
tions (a 225–265 C temperature and 2.9–5.6 MPa pressure) if
a catalyst is used.138 The wet biomass is almost completely
gasied without pre-drying using hydrothermal gasication.
The heating value of the resulting gas product depends on the
reaction conditions.139
Hydrothermal gasication can be classied in three main
regions depending on the temperature and pressure (Fig. 12).
Region 1: catalytic gasication (275–550 C).
Region 2: supercritical gasication (374–700 C).

Region 3: high temperature gasication (550–700 C).
4.2.4.4. Hydrothermal liquefaction. Hydrothermal liquefac-
Fig. 12 Properties of water and the uses of hydrothermal tion is a thermochemical process oen used to obtain a liquid
techniques.131 product, called a bio-oil, at moderate temperatures and under
high pressures.140 This process produces a bio-oil with an upper
heating value of 35–40 MJ kg1, an aqueous phase containing
to increase the carbon content of biomass and obtain a higher dissolved organic compounds, a solid (called char), and a gas
caloric value.133 Biomass with a high moisture content can be rich in CO2.141,142 The purpose of this process is to decompose
converted to fuel within a few hours in water at 180–250 C and biomass with a high moisture content into small molecules and
under a 2–10 MPa pressure.115,133 The HTC process has been reduce the biomass oxygen content to obtain liquid fuels or
found to allow the formation of nano and microsized carbon valuable chemicals.143,144 During the hydrothermal liquefaction
particles with various properties, such as high energy value, process, biomass and oxygen are rapidly oxidized or mineral-
high chemical and thermal stability.115,134–136 It is accepted that ized to form CO2 or H2O, while harmful combustion products,
hydrolysis, dehydration, decarboxylation, aromatization, and such as NOx, are converted into harmless products in a hydro-
condensation polymerization occur during hydrothermal thermal environment.145 In a hydrothermal environment, water-
carbonization.133 soluble portions are dissolved at approximately 100 C, and
4.2.4.3. Hydrothermal gasication. The gasication process extraction can be performed. Hydrolysis occurs above 150 C;
is an effective thermochemical method for converting biomass polymers such as cellulose, hemicellulose, and protein are
into gas products, such as carbon monoxide (CO), hydrogen decomposed into oligomers and/or monomers. At approxi-
(H2), carbon dioxide (CO2), and methane (CH4).137 Gasication mately 200 C and under 1 MPa pressure, the biomass turns
into a sludge.139 Liquefaction is usually performed at
Table 8 The dielectric constant of water depends on the temperature and pressure changes
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a temperature range between 280 C and 380 C and under compounds as well as their amounts are signicantly affected
a pressure range between 7 and 30 MPa for 10 to 60 minutes.116 by operating conditions (Table 9). Moreover, the product
The reactions that occur during hydrothermal liquefaction are selectivity can be accomplished by using catalysts.168
as follows: larger molecules of the biomass are hydrolyzed and/ Several studies have been carried out to propose the
or decomposed into smaller molecules. Since the majority of decomposition pathway of lignin under hydrothermal condi-
the resulting molecules are unstable and reactive, they may tions.169–171 The results demonstrated that fragmentation and
recombine with larger molecules. Furthermore, a considerable condensation reactions are competitive under hydrothermal
portion of the oxygen in the biomass is removed by dehydration conditions. The main steps occur in hydrothermal decomposi-
or decarboxylation.140 tion of lignin are hydrolysis and cleavage of the ether bond and
The parameters affecting the hydrothermal liquefaction the C–C bond, demethoxylation, and alkylation.171 b-Ether
performance (such as the bio-oil yield, char formation, bio-oil cleavage takes place primarily. Phenolic monomers and dimers
composition, H/C ratio, oxygen content, pH value, and upper form by the initial cleavage of the ether bond. The prominent
heating value) include the biomass type, temperature, pressure, oxygenated hydrocarbons from hydrothermal decomposition of
holding time, particle size, biomass/solvent ratio, reaction lignin are phenol, guaiacol and catechol in most studies.172–176
atmosphere, reducing agent and catalyst.146 These parameters Guaiacol is the predominant compound that observed in bio-
are explained below. oils from the hydrothermal degradation of lignin.175 Catechol
The biomass type is one of the most important parameters and phenol produced from the demethoxylation of guaiacol
affecting hydrothermal liquefaction. The products obtained under hydrothermal conditions.177 Notably, the demethox-
from liquefaction vary depending on the biomass components ylation and alkylation reactions are favored at high tempera-
and the amount of these components. High cellulose and tures (i.e., 270–330 C). Other phenolic compounds detected
hemicellulose contents of biomass usually provide higher bio- from the hydrothermal decomposition of lignin were phenol, m/
oil yields, while a high lignin content reduces the yield of bio- p/o-cresol, guaiacol, 2-/4-ethylphenol, veratrol, methylguaiacol,
oil and increases the biochar amount.145,147,148 catechol, 4-methylcatechol, 4,5-dimethylresorcinol and syringol
Cellulose, a major component of lignocellulosic biomass, (Table 9).
has got much attention for the processing in hydrothermal Besides lignin and cellulose, lignocellulosic biomass has
media. Several studies regarding deconstruction of cellulose also been widely used as feedstock for the hydrothermal
have been carried out in hydrothermal media.149–155 These liquefaction. Some commonly employed lignocellulosic
studies demonstrated that cellulose rst dissociate into water- biomasses as feedstocks for the non-catalytic hydrothermal
soluble oligomers and monomers. The monomers and oligo- liquefaction are beech wood, spruce wood, hazelnut shell,178
mers undergo further degradation to form bio-oil, water soluble pine wood,179–181 Chinese r wood,148 Manchurian ash,148
products, char and gas.109 To understand the deconstruction Chinese red pine wood,148 Chinese white poplar wood,148
pathway of cellulose under hydrothermal conditions, glucose cornelian cherry stones,182 corn straw,183 peanut straw,184 rice
has been widely used as a model compound.149,156–162 The above straw184 and soybean straw.184 It can be observed from Table 10,
studies demonstrated that decarbonylation and decarboxyl- the bio-oil yields changes depending on the feedstock as well as
ation reactions are negligible and play minor role in the operating conditions.
decomposition of cellulose under hydrothermal conditions. Besides lignocellulosic biomass, algal biomass has been
Srokol et al. investigated hydrothermal reactions of diluted widely used as feedstock for the production bio-oils from the
solutions (50 mM) of glucose, fructose, mannose and galactose non-catalytic hydrothermal liquefaction. Algal biomass is
for longer reaction times (25–200 s) at 340 C and 27.5 MPa.162 It composed of proteins, polysaccharides, lipids, and inorganic
was shown that both acid and base catalyzed reactions play components. It is an attractive renewable biomass resource due
a role during the initial stages of the hydrothermal liquefaction to its exible growth options (i.e., growing algae on wastewater,
of cellulose. The acid-catalyzed reactions were mainly dehy- non-arable land with brackish or in a marine environ-
drations in which HMF is the major intermediate. Hydro- ment).185,186 Table 11 provides the highest bio-oil yields from
thermal liquefaction of cellulose was carried out under acidic, various algal biomasses including microalgae and macroalgae
neutral and alkaline conditions.163 The major product was HMF via hydrothermal liquefaction process. Some commonly used
under acidic and neutral conditions whereas C2–5 carboxylic microalgae biomasses for the non-catalytic hydrothermal
acids were obtained under alkaline conditions. During the liquefaction of biomass are Nannochloropsis sp.186, Nanno-
initial stages of the hydrothermal liquefaction of cellulose, chloropsis gaditana,187,188 Nannochloropsis salina,189 Scenedesmus
fragmentations take place in base catalyzed reactions via retro- almeriensis,187,188 Spirulina platensis,190,191 Chlorella vulgaris,187,192
aldol condensation and beta elimination. Hydrothermal lique- Dunaliella tertiolecta,187,193 Galdieria sulphuraria189, Porphyridium
faction of cellulose mainly yields furfurals, ketones, and purpureum,187 Tetraselmis sp.194 and Tetraselmis suecica.187
acids.163–168 Recent studies demonstrated that phenolic Typical macroalgae biomasses for the non-catalytic hydro-
compounds such as phenol, alkylphenols, catechol, acids and thermal liquefaction of biomass are Enteromorpha pro-
esters were also detected compounds in biocrudes from the lifera,195,196 Laminaria saccharina,197 Sargassum patens C.
hydrothermal liquefaction of cellulose.166,167 It is considered Agardh,198 and Macrocystis sp.199 The hydrothermal liquefaction
that condensation of reaction intermediates (such as furfurals) of microalgae produces high yields of bio-oils. Macroalgae has
produced phenols or acids.166 Notably, the type of formed high ash content and low lipid content. Thus, it yields lower bio-
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Table 9 Hydrothermal liquefaction (HTL) of lignin and cellulose at different process conditions
Temperature Residence time

Component of biomass ( C) (min) Pressure (MPa) Main ndings Reference
Kra lignin from sowood 350 11 25 (observed) The experiments were carried out with 172
(LignoBoost kra lignin) phenol in the presence of K2CO3 (0.4–
2.2 wt%). The biocrude contained mainly
phenolic species including (phenol,
anisole, 2-/4-methyl anisole, 2-
ethylanisole, m/p/o-cresol, guaiacol,
methylguaiacol, 4-ethylguaiacol, 4-
propylguaiacol, 2-ethylphenol,
dimethylphenol, 2-acetylphenol, 4-
ethylphenol, propylphenol, catechol, 4-
methylcatechol, 4-ethylcatechol and
phenolic dimers)
Kra pine lignin Indulin® AT 280–350 15 18.1–24 The experiments were carried out 173
(observed) without and with phenol in the presence
of K2CO3 (1.7 wt%). Biocrude consisted of
mainly phenols including phenol, m/p/o-
cresol guaiacol, 2-/4-ethylphenol,
veratrol, methylguaiacol, catechol, 4-
methylcatechol, hydrocoumarine,
vanillin, and phenolic dimers. The use of
phenol in the HTL runs increased the
total amount of phenols
Soda wheat straw lignin 300 30 17 (observed) The experiments were conducted in the 174
(protobind 1000) presence of 18.6 g 0.5 M NaOH. The
selected phenolic compounds were
quantied. The quantied phenolic
species were anisole, phenol, guaiacol,
catechol, 3-methoxycatechol, 1,2-
dimethoxybenzene, 1,2,3-
trimethoxybenzene, syringol, vanillin
and acetosyringone. The amount of
guaiacol, catechol, and 3-
methoxycatechol was high
Alkaline lignin 280 15 N/A The experiments were carried out 175
without using any catalysts. The
identied prominent compounds in bio-
oil were mainly phenols including
guaiacol, 4-methyl guaiacol, 4-ethyl
guaiacol, phenol, 4-mehylphenol,
catechol, 3-/4-methyl catechol, and 4,5-
dimethylresorcinol. Among identied
compounds guaiacol had the highest
peak area
Corncob lignin 210–290 0–40 N/A The non-catalytic hydrothermal 176
degradation of lignin mainly yielded
phenolic compounds. The identied
volatile organic compounds in the
biocrude were phenols and its derivatives
(i.e., phenol, 3-,4-methylphenol, 2-
ethylphenol, 4-ethylguaiacol, syringol, 2-
methoxy-4-propyl-phenol, and 2-
methoxy-4-(1-propenyl)phenol). Among
the identied compounds, 4-
ethylguaiacol, phenol, and syringol were
prominent with high peak areas
Cellulose 275–320 0–30 N/A Hydrothermal liquefaction of cellulose 163
was carried out at different pHs. The
identied compounds were
hydroxymethylfurfural (HMF), acetic
acid, propinoic acid, isobutyric acid,
butyric acid, iso-valeric acid, isocaproic
acid, n-caproic acid, heptanoic acid,
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Table 9 (Contd. )
Temperature Residence time

Component of biomass ( C) (min) Pressure (MPa) Main ndings Reference
lactic acid, levulinic acid, and

dihydroxyacetone. The major compound
was HMF at pH 3 and pH 7 whereas this
compound did not observe at pH 14
Microcrystalline cellulose 185–195 25–110 3.8–5.4 MPa Microwave assisted non-catalytic 165
(observed) degradation of cellulose produced two
major products namely HMF and
glucose. The product selectivity and

yields changed depending on the
operating conditions
Cellulose (microcrystalline, 350 30 N/A Non-catalytic hydrothermal liquefaction 166
Alfa Aesar) of cellulose produced the following
products: phenols, ketones and
aldehydes, hydrocarbons, alcohols, and
acids and esters
Cellulose (medium bers) 240–320 30 N/A Non-catalytic hydrothermal liquefaction 167
of cellulose yielded aldehydes, ketones,
acids, and phenols
Cellulose (Avicel® PH-101) 250 60 1.0 (initial) Hydrothermal liquefaction of cellulose 168
without and with catalyst (i.e., Fe powder,
FeOx, Fe powder + Pd/Al2O3). The water-
soluble (WS) fraction from the non-
catalytic run contained 2-butanone, 2-
pentanone, 3-hydroxy-2-butanone,
hydroxyacetone, furfural, acetic acid, 2,5-
hexanedione, 2,3-butanediol, 3-methyl-
1,2-cyclopentanedione, and levulinic
acid. Fe assisted HTL of cellulose mainly
produced hydroxyketone while diols
formed in WS fraction with the use of Fe
+ Pd/Al2O3
oil yields relative to microalgae biomass. As can be seen from hydrolytic cleavage of the ester bonds in lipids, peptide bonds in
Table 11, the bio-oil yield signicantly changes depending on proteins, and glycosidic ether bonds in carbohydrates can be
the type of algal biomass. accelerated using catalysts in hydrothermal environments.144,204
Temperature is one of the decisive parameters of hydro- Two types of catalysts, heterogeneous and homogeneous, are
thermal liquefaction.200 The initial temperature increase in this oen used. Homogeneous catalysts may have a higher activity
process increases the bio-oil yield, while a further temperature than heterogeneous catalysts.204 However, it is oen difficult to
increase triggers gasication and reduces the bio-oil yield.145 recover homogeneous catalysts at the end of the reaction.144
Under subcritical conditions, the temperature increase usually When the concentration of the homogeneous catalyst is below
leads to a bio-oil with a low oxygen content.201 The widely used a critical value, the bio-oil yield increases and the solid content
temperature range is from 250 C to 350 C, and the maximum decreases with increasing the catalyst concentration; exceeding
bio-oil yield is usually achieved at approximately 280–310 C. this critical value decreases the bio-oil yield and increases the
Studies performed with several wood derivatives using the 280– solid content.147 Alkaline salts increase the bio-oil yield and
360 C temperature range show that a temperature increase up reduce the solid content under subcritical conditions, while
to 300 C, the optimum temperature, leads to an increase in the acids increase the production of water-soluble products (such
bio-oil yield, while a further increase in the temperature leads to as sugars, carboxylic acids, furfural, and 5-hydrox-
decreased yields.148,202 Very high temperatures are not appro- ymethylfurfural).140,205 Generally speaking, hydrothermal lique-
priate for bio-oil production in terms of both operating costs faction of lignocellulosic biomass with heterogenous catalyst
and bio-oil yield. Notably, hydrothermal liquefaction of algal produce lower yields of bio-oils than those with homogenous
biomass requires temperatures higher than 300 C for high bio- catalysts.22,206–213 The reason is that a heterogeneous catalyst is
oil yields (see Table 11). most likely affected by sintering, poisoning, internal diffusion
Catalysts play an important role in improving bio-oil prop- limitation, and inactivation in the hydrothermal liquefaction of
erties. The functions of catalysts include increasing the H/C biomass.212 Heating values of bio-oils obtained with heteroge-
ratio of the bio-oil, reducing the bio-oil viscosity, and nous catalyst are comparable than those with homogenous
removing heteroatoms (such as O, N, and S) in bio-oils.203 The (Table 12). Notably, extraction procedure and solvent type for
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Table 10 Non-catalytic hydrothermal liquefaction of various lignocellulosic biomasses
Temperature Residence time The highest bio-oil

Lignocellulosic biomass ( C) (min) Pressure (MPa) yield (wt%) Reference
Beech wood 377 25 N/A 28.4 178

Spruce wood 377 25 N/A 25.8 178
Hazelnut shell 377 25 N/A 22.1 178
Pine wood 300 15 2 40.0 179
Pine wood 260 0 Atmospheric 14.1 180
Pine wood 350 10 0.5 38.4 181
Chinese r wood 320 10 N/A 23.8 148
Manchurian ash 300 10 N/A 30.7 148

Chinese red pine wood 340 10 N/A 20.6 148
Chinese white poplar wood 300 10 N/A 26.4 148
Cornelian cherry stones 300 0 Atmospheric 28.0 182
Corn straw 300 0 4.1 29.3 183
Corn straw 320 60 0.11 7.9 184
Peanut straw 320 60 0.11 14.7 184
Rice straw 320 60 0.11 15.1 184
Soybean straw 320 60 0.11 15.8 184
Table 11 Non-catalytic hydrothermal liquefaction of various algal biomasses
Temperature Residence time The highest bio-oil

Algal biomass ( C) (min) Pressure (MPa) yield (wt%) Reference
Nannochloropsis sp. 350 60 N/A 43.0 186

Nannochloropsis gaditana 375 5 0.5 54.3 187
Nannochloropsis gaditana 350 15 2 60.0 188
Nannochloropsis salina 350 60 1.4 59.1 189
Scenedesmus almeriensis 375 5 0.5 58.1 187
Scenedesmus almeriensis 350 15 2 57.7 188
Spirulina platensis 350 30 Atmospheric 38.0 190
Spirulina platensis 300 60 N/A 41.9 191
Chlorella vulgaris 375 5 0.5 55.3 187
Chlorella vulgaris 350 60 N/A 23.0 192
Dunaliella tertiolecta 375 5 0.5 55.3 187
Dunaliella tertiolecta 320 30 N/A 48.9 193
Galdieria sulphuraria 350 30 1.4 31.0 189
Porphyridium purpureum 375 5 0.5 47.1 187
Tetraselmis sp. 350 5 N/A 65.0 194
Tetraselmis suecica 375 5 0.5 45.6 187
Enteromorpha prolifera 300 30 2 20.4 195
Enteromorpha prolifera 370 40 N/A 32.3 196
Laminaria saccharina 350 15 N/A 19.3 197
Sargassum patens C. Agardh 340 15 3 32.1 198
Macrocystis sp. 350 30 5 19.2 199
the extraction of biocrudes as well as the type of raw material challenges for the homogenous catalysts used in hydrothermal
have signicant effect on the resulting biocrude yields obtained biomass processes.
from hydrothermal liquefaction process. Homogenous catalyst Like lignocellulosic biomass, algal biomass has also been
such as potassium carbonate (K2CO3) is known to promote hydrothermally processed with base and basic salts.196–198,214 In
water gas shi (WGS) and steam reforming reactions as well as contrast to lignocellulosic biomass, the use of base and basic
gasication under sub- and supercritical conditions.122 The salts on the hydrothermal liquefaction of algal biomass had
reason is that the presence of carbonate/bicarbonate increases either negative effect or a very little positive effect on bio-oil
hydrogen production due to changes in the gaseous equilib- yields.196–198,214 A previous work demonstrated that a heteroge-
rium and accelerates WGS as well as steam-reforming reac- nous catalyst could improve the bio-oil yields.215 A wide range of
tion.122 Heterogeneous catalysts usually have positive effects on heterogenous catalyst for the hydrothermal liquefaction of
gasication processes performed at low temperatures.140 Nannochloropsis sp. at 350 C and 1 h were investigated.215 The
Moreover, the catalyst separation, recovery and reutilization are tested catalysts were metal supported carbon (Pd/C, Pt/C, Ru/C),
important for industrial applications, which are major sulded CoMo/g-Al2O3, one transition metal catalyst supported
View Article Online
on silica-alumina (Ni/SiO2–Al2O3), and zeolite. In the absence of

Table 12 Yield (wt%), elemental composition (wt%), and HHV (MJ kg1) of the bio-oils produced from the hydrothermal liquefaction of various lignocellulosic biomasses in the presence of
HHVf (MJ kg1)
Microwave assisted hydrothermal liquefaction. e By difference. f HHV was calculated according to the Dulong formula that is HHV ¼
added H2, all tested catalysts produced higher yields of crude
bio-oil than that of the non-catalytic run. The highest bio-oil
yield was 57 wt% and obtained with Pd/C.
40.92
39.25
26.00
26.31
31.49
28.11
29.51
29.49
28.42
27.71
19.10
25.21
24.30
The bio-oil yield from the non-catalytic run was 35 wt%. The
bio-oil yields from other catalysts ranged from 45 to 50 wt%.
Oe (wt%)
There are some interactions between the solvent molecules

5.00
7.40
28.14
27.31
19.42
23.70
23.55
23.05
24.79
25.77
39.10
30.80
30.5
and the biomass in hydrothermal medium, and the dissolution
of the biomass components is suppressed as the biomass/
N (wt%)
solvent ratio increases during the hydrothermal process.147 A

low bio-oil yield is achieved, since the limited amount of water

1.60
1.60
0.06
0.09
0.05
0.09
—
—
—
—
—
—
—
does not form a good suspension with the biomass, thereby
delaying liquefaction in the reactor.216 Very high biomass/
H (wt%)
solvent ratios support more gas production, as observed

9.40
9.00
6.20
6.10
7.08
6.01
7.22
6.97
6.82
6.62
6.30
6.71
5.80
during pyrolysis.147 On the other hand, low biomass/solvent
ratios enhance biomass conversion and lead to high bio-oil
C (wt%)
69.23c
69.98c
yields; unfortunately, this is not economical.201 However, the

84.00
82.00
65.60
66.50
73.50
70.29
68.34
67.54
54.70
62.49
63.60
bio-oil yield has been observed to decrease at very low biomass/

solvent ratios.217
Yield (wt%)
Although smaller particles with a large surface area can yield

more bio-oil, as small particles can be highly hydrolyzed,218
29.8c
31.0
42.0
38.5
39.5
36.3
31.9
41.9
43.0
13.9
16.0
28.1
34.4
reducing the particle size requires more energy. Thus, it is

important to work with the most appropriate particle size.
Reaction time
Water acts as both a heat transfer medium and an extractor in

hydrothermal environments, which renders the hydrothermal
liquefaction process relatively insensitive to particle size;
(min)
112.8
therefore, it is not necessary to reduce the particle size

10
10
30
30
10
10
30
30
30
0
0
excessively.145
T ( C)
A reaction atmosphere may have various effects on the bio-

400
400
300
300
360
360
300
300
300
300
250
300
300
oil yield and oxygen content.204,219 Since air causes the

combustion of biomass, a low bio-oil yield is obtained under
air.145,148,219 Reducing gases (CO and H2) and inert gases (N2) are
Iron powder (10 wt% of the biomass)
Co-precipitated Ni–Co/Al–Mg catalyst

NaOH (NaOH/biomass ratio ¼ 0.40)
NaOH (NaOH/biomass ratio ¼ 0.40)
more favorable for obtaining large amounts of bio-oil.219 These

KF/Al2O3 (20 wt% of the biomass)
KF/Al2O3 (20 wt% of the biomass)
t-BuOK (10 wt% of the biomass)
Na2CO3 (5 wt% of the biomass)
gases have important functions, including stabilizing the

K2CO3 (5 wt% of the biomass)
Synthetic hydrotalcite (5 wt%)

KOH (10 wt% of the biomass)
KOH (5 wt% of the biomass)
decomposed liquid products and preventing the cyclization,

concentration, or repolymerization of free radicals,147 which
inhibits char formation and achieves high bio-oil yields.
Colemanite (10 wt%)
Numerous studies have been performed to determine the effect

of the reaction atmosphere and other liquefaction parameters
on the hydrothermal liquefaction process, and although
(25 wt%)
d
Catalyst
signicant progress has been made, the mechanisms of action

Non-pretreated. b Alkaline pretreated. c Heavy bio-oil.
of these parameters have not been fully established.201 This is

because the structure of biomass is complex, and it is difficult to
control the reactions in the hydrothermal environment.
A mixture of pine and spruce biomassd
homogeneous and heterogenous catalysts
The holding time is dened as the time required to maintain

the maximum temperature of HTL and does not include the
heating and cooling times.200 The holding time is an important
0.338C + 1.428(H O/8) + 0.095S.
factor that affects bio-oil production and biomass conversion.201

The holding time determines the composition of the liquefac-
Type of lignocellulose
tion products and conversion rate of biomass.147 While the bio-

Scotch pine wood
Scotch pine wood
Paulownia wood
Paulownia wood
oil yield increases up to the optimum reaction time, the liquid

Willow wooda
Willow woodb
Spruce wood
products may re-decompose into gas products and repolymerize

Beech wood
Beech wood
Birch wood
Birch wood
Birch wood
into solid products as the reaction time increases further.204 The

heat loss per unit mass of the bio-oil produced using prolonged
heating times is signicantly higher than that of a bio-oil
produced with shorter heating times.220 A fast heat-up period
Ref.
207
207
208
208
209
209
210
210
213
206
22
22
22
and short holding times have positive effects on bio-oil yields.

a
View Article Online
With this aspect, hydrothermal liquefaction of lignocellulosic gases (i.e., H2, H2/CO) are effective to inhibit the char formation
biomass is similar to the fast pyrolysis of lignocellulosic during HTL processing.114,145,232 Formic acid was also employed
biomass.221 Holding times can vary between 0 and 30 min to as an in situ hydrogen donor for the reductive de-polymerization
obtain high bio-oil yields.201 Thus, high bio-oil yields were of kra lignin (KL).233 KL was effectively depolymerized at
achieved at short holding times in most studies at which 300 C, 1 h, and in a mixture of water–ethanol. It was also
hydrothermal liquefaction of lignocellulosic biomass have been demonstrated that formic acid was more reactive hydrogen
carried out.167,174,183,222–224 Most studies related to the hydro- source than external hydrogen for reductive depolymerization
thermal liquefaction of lignocellulosic biomass have been of KL. Hydrothermal liquefaction of lignocellulosic biomass can
carried out using batch autoclaves.225 However, long heating up be carried out by the addition of both reducing gas in the form
periods are required to reach desired temperatures ($275 C) of syngas (60% CO–40% H2) and an alkali catalyst (10 wt% on
which is the major drawback of batch autoclave experiments. wood basis) as an aqueous solution.95 However, some noble
The holding time in the hydrothermal liquefaction of ligno- metal catalyst together with hydrogen donors and an alkaline
cellulosic biomass have also effect on the bio-oil compositions. may be required for the effective depolymerization of
Higher molecular weight fractions decrease, and the amount of lignocellulose.
lower molecular weight fractions increase at long holding 4.2.4.5. Continuous hydrothermal liquefaction of biomass at
times.226 In the meantime, long holding periods during hydro- a glance. Most of the hydrothermal liquefaction of biomass
thermal liquefaction lead to increase the bio-char yields as well works have been carried out using batch autoclaves as they are
as carbon contents in bio-chars due to the repolymerization easy to operate and appropriate for a range of biomass feed-
reactions. stock.156,234–238 The use of relatively high dry matter content in
High heating rates lead to the formation of gaseous products batch autoclaves for the hydrothermal liquefaction process is
due to re-decomposition reactions, while low heating rates the most signicant advantage.239 However, there are some
usually lead to the formation of char due to the repolymeriza- drawbacks working with batch autoclaves for the HTL of
tion of intermediates.227 Therefore, moderate heating rates biomass. Batch processes at a large scale have limitations in
should be preferred to overcome heat transfer limitations and heat transfer, which result in long heat up periods. Temperature
achieve high bio-oil yields.228 Zhang et al. carried out hydro- and pressure should be considered as a single parameter as
thermal liquefaction of biomass at the following process operating pressures change depending on the temperatures.
conditions: 300–450 C temperature, 1–30 min holding time, Batch autoclave processes for hydrothermal liquefaction is not
and 5–140 C min1 heating rate.229 The bio-oil yield increased considered as applicable for industrial applications due to high
from 61% to 65% when the heating rate was increased from 5 to operating costs. In this context, continuous hydrothermal
14 C min1. Notably, bio-oil compositions are not much liquefaction of lignocellulosic biomass has come to the fore-
effected by changing the heating rates due to the high stabili- front in terms of applicability of the industrial practice.
zation property of hot compressed water.230 Continuous hydrothermal liquefaction of biomass dates to
Generally, pressure is maintained above saturation pressure 1970's.240 The process is also known as direct liquefaction of
to keep water in liquid phase (subcritical water) during HTL biomass. In this process, biomass slurries containing 5–35%
process. Pressure helps to maintain the single-phase environ- solid are pumped and hydrolyzed at the elevated temperatures
ment of the liquefaction process.228 A high pressure increases and pressures. Unlike batch autoclave test, temperature and
the solvent density and solubility of the biomass components, pressure can be controlled separately in continuous-ow reac-
and the solvent spreads more efficiently into the molecular tors.239 High pressure systems are essential to provide larger
structure of biomass, thereby increasing the biomass decom- ow rates of biomass slurry. This is important to obtain bio-oil
position and degradation degree.231 In the subcritical region, yield efficiently. However, pumping biomass slurries at high
the increased pressure leads to an increased water density. solid concentrations can lead to plug the orices and valves.
High-density water can penetrate the biomass structure more This can be overcome, to some extent, by pre-hydrolyzing of
easily than low-density water, which increases the bio-oil yield biomass slurry. A number of studies have investigated contin-
and biomass degradation.146 In the supercritical region, an uous hydrothermal liquefaction of biomass. Most of these
increased pressure has a limited effect on the properties of the attempts were commercial scale-up of this technology. Hydro-
water environment; no signicant change occurs in terms of the thermal liquefaction of biomass has been carried out at the
bio-oil yield, in particular.145 Under supercritical conditions, an following conditions in the Lawrence Berkeley Laboratory [LBL],
increased pressure causes an increase in the solvent density, USA:241 Douglas r wood slurry (18 wt%), Na2CO3 (13 wt%),
which creates a cage effect for C–C bonds and prevents the C–C reducing gas (carbon monoxide–hydrogen), 330–360 C hydro-
bonds from breaking.227 One can conclude that the pressure thermal liquefaction temperature, 205–232 atm pressure, 10–
may have insignicant or negative effect on overall bio-oil yields 24 h run time, and 0.9–1.2 (kg h1) slurry feed rate. The bio-
at the supercritical conditions. However, it was reversed under crude yield ranged from 27 to 33 wt% and contained mono-
subcritical conditions. meric and dimeric phenols, semi polar aromatics and aromatic
Reducing agents are oen used to hinder the repolymeriza- hydrocarbons. The Pittsburgh Energy Research Center (PECR)
tion and condensation of fragmented radicals, which helps the has established the Albany plant.95 The bio-crude was produced
inhibition of char formation. Hydrogen donor solvents with at 340 C, 204 atm, 13 wt% Na2CO3 catalyst and the
(ethanol, methanol, tetralin, propanol, tetralin) and reducing
View Article Online
presence of reducing gas (carbon monoxide–hydrogen). The 5. Conclusion

bio-oil yield was about 22 wt%.
In another process, called hydrothermal upgrading This review describes all the steps of biomass processing,
(HTU®), hydrothermal liquefaction of biomass was carried out explaining the chemistry taking place in the background of the
at 300 and 350 C, pressures 100–180 bar and a residence time processes in a comprehensive manner. Hydrothermal and
ranging from 5 to 20 minutes.242 In this process, biomass is pyrolysis processes are two main routes that are commonly used
rst preheated at 80 C. Subsequently, the water/feedstock in the utilization of biomass. Although each thermochemical
mixture is pressurized by a pump to 10–20 MPa. The process has its own advantages and disadvantages, hydro-
biomass slurry is heated to 300–350 C for 5–20 min. It was thermal biomass processing has several advantages in
demonstrated that the high oxygen removal from 22 to 50% or comparison with other thermochemical processes such as the
higher was possible with this process without using catalyst or pyrolysis. In hydrothermal media, the physicochemical prop-
reducing gas. HTU of onion waste yielded 38 wt% bio-oil.95 The erties of water change during the thermal treatment and differ
work at Pacic Northwest National Laboratory (PNNL) focused from those of ambient water. Thus, water acts as an acidic and
on the hydrothermal liquefaction of various biomasses in basic catalyst in reaction environments due to H3O+ and OH
a continuous-ow reactor.243,244 In those studies, the bio-oil ions, which makes it an excellent solvent and reaction medium.
products were recovered directly by gravity separation from Any biomass and waste generated by the agriculture and food
the aqueous phase. HTL of the grape pomace was carried out industries and plants, and aquatic biomass such as algae can be
at 350 C, 20.1 MPa pressure, 3.3 h residence time, and with no processed in hydrothermal media. The hydrothermal process-
catalyst.243 The biocrude yield on carbon base ranged from 50 ing is applicable for any type of biomass as well as waste
to 56 wt%. Hydrothermal liquefaction of wet macroalgal treatment. However, the moisture content of the biomass
slurries (5–22 wt% dry solids) was carried out at 350 C, 20 MPa should be less than 10 wt% for the pyrolysis process which is an
pressure with a liquid hourly space velocity ranging from 1.2 to additional cost. In contrast to biomass pyrolysis process, the
1.5 L of slurry per liter of reactor volume per hour.244 The operating temperatures that is generally used in hydrothermal
highest bio yield was about 28 wt% (60% on a carbon basis) biomass processing is relatively low. Moreover, the operating
and obtained at feed concentration of 22 wt% dry solid. conditions can be easily adjusted with using the same equip-
Researchers from Denmark reported the continuous hydro- ment for the target product. Besides these advantages, there are
thermal co-liquefaction of aspen wood and glycerol.245 The also some disadvantages in hydrothermal process. The
following experimental conditions were applied: 400 C handling of large volumes of water and the use of complex and
temperature, 30 MPa pressure, feed (16.9 wt% aspen wood, expensive reactors are the main drawbacks. Compared to
15.7 wt% glycerol, and 62.3 wt% water) with the use of 4.2 wt% pyrolysis process, the separation and extraction procedure to
K2CO3. The bio-oil products were recovered directly by gravity recover bio-oils in the hydrothermal processing of biomass is
separation from the aqueous phase. Biocrude yield on carbon tedious. The plant for the hydrothermal biomass processing
basis ranged from 62 to 66 wt%. Biocrude was composed of requires high investment cost. The bio-oil products from the
oxygenated cyclic compounds having carbon atoms in the hydrothermal liquefaction can be used as high-value chemicals,
range of C6–C21. Studies in a lab-scale continuous-ow reactor as fuel precursor or platform chemicals for synthesizing other
at University of Illinois investigated hydrothermal processing commercial products. The products from the hydrothermal
of swine manure.246,247 The experiments were carried out at carbonization of biomass have high potential to be used as
285–305 C temperature, 9–12.1 MPa pressure, and 40–80 min important nano and microsized carbon particles with various
residence time. The highest biocrude yield and the highest properties, such as a high energy value, a high chemical and
heating value were 70 wt% and 31 MJ kg1, respectively and thermal stability, and an increased surface area and adsorption
obtained at 305 C, 10.3 MPa, and 80 min. Recently, the capacity. Gases produced from the hydrothermal gasication
Danish-Canadian Company (Steeper Energy) in collaboration can be used to generate electricity, heat, chemicals and liquid
with Aalborg University, Denmark has developed the Hydro- fuels. All the attractive and unique features make the “hydro-
faction™ technology.122 The Hydrofaction™ process, contrary thermal processing of biomass” a good candidate for converting
to most hydrothermal liquefaction processes, is carried out biomass into value-added products, and this hydrothermal
above the critical point of water at 30–35 MPa and 390–420 C. process has become an irrevocable alternative technology used
In this process, wood slurry (a feed concentration of 17– to produce biofuels from various biomasses.
20 wt% dry solid) of at 30–35 MPa and 390–420 C with the use
of K2CO3 as catalyst were converted into bio-oils. The most Conflicts of interest
distinct feature of this process is recirculation of aqueous
phase containing water, water-soluble organics, and a dis- There are no conicts to declare.
solved homogeneous catalyst. This step increases the homo-
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Sustainable Energy and Fuels From Biomass

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Sustainable

Energy & Fuels

Sustainable energy and fuels from biomass:

domestic product (GDP). According to the Energy Information

Dr Koray Alper got his bachelor's Dr Kubilay Tekin received his

Sustainable Energy & Fuels Review

Dr Selhan Karagöz was born in Dr Arthur J. Ragauskas held the

Review Sustainable Energy & Fuels

yields and selectivity.24–26 This study provides a comprehensive

largely ignored.30 Although conventional energy resources

Sustainable Energy & Fuels Review

Fig. 4 Primary and secondary energy resources.

Review Sustainable Energy & Fuels

Table 3 Pros and cons of nonrenewable energy resources47

Table 4 Pros and cons of renewable energy resources47

Sustainable Energy & Fuels Review

Review Sustainable Energy & Fuels

3.1.2. Hemicellulose. Hemicellulose, the second most

Sustainable Energy & Fuels Review

Fig. 8 Structure of cellulose.

Fig. 9 Building blocks of hemicellulose.

Review Sustainable Energy & Fuels

Fig. 10 Lignin monomer compositions.

Sustainable Energy & Fuels Review

Fig. 11 The compositions of stilbenes, terpenes, and ﬂavonoids.

Review Sustainable Energy & Fuels

sures (5–40 MPa) in liquid or supercritical water.108 Water is

Table 5 Pyrolysis techniques101

Reaction time Heating Temperature ( C) Main product

Carbonization Hours-days Very slow 400 Biochar

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as follows: initiation, hydrogen transfer, radical isomerization,

Normal water Subcritical water Supercritical water

Temperature ( C) 0–100 100–374 >374

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is usually performed within a temperature range of 400 and

Region 2: supercritical gasication (374–700 C).

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Temperature Residence time

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Temperature Residence time

lactic acid, levulinic acid, and

glucose. The product selectivity and

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Table 10 Non-catalytic hydrothermal liquefaction of various lignocellulosic biomasses

Temperature Residence time The highest bio-oil

Beech wood 377 25 N/A 28.4 178

Manchurian ash 300 10 N/A 30.7 148

Table 11 Non-catalytic hydrothermal liquefaction of various algal biomasses

Temperature Residence time The highest bio-oil

Nannochloropsis sp. 350 60 N/A 43.0 186

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on silica-alumina (Ni/SiO2–Al2O3), and zeolite. In the absence of

HHVf (MJ kg1)

There are some interactions between the solvent molecules

solvent ratio increases during the hydrothermal process.147 A

low bio-oil yield is achieved, since the limited amount of water

solvent ratios support more gas production, as observed

yields; unfortunately, this is not economical.201 However, the

bio-oil yield has been observed to decrease at very low biomass/

Although smaller particles with a large surface area can yield

HHVf (MJ kg1)