BiomassConversiontoFuelsandValue Addedchemicals

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Biomass Conversion to Fuels and Value-Added Chemicals: A Comprehensive

Review of the Thermochemical Processes
Article · October 2019

DOI: 10.2174/2405463103666191022121648
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Current Alternative Energy, 2020, 4, 1-23 1
REVIEW ARTICLE
Biomass Conversion to Fuels and Value-added Chemicals: A Comprehen-

sive Review of the Thermochemical Processes
Erasmus Muh1,*, Fouzi Tabet2 and Sofiane Amara3
1
Pan African University, Institute of Water and Energy Sciences (including Climate Change), BP 119 Tlemcen 13000,
Algeria; 2DBFZ-Deutsches Biomasseforschungszentrum Gemeinnützige GmbH, Torgauer Straße 116, D-04347 Leipzig,
Germany; 3Unité de Recherche Matériaux et Energies Renouvelables (URMER), University of Tlemcen, BP119 Tlemcen
13000, Algeria
Abstract: Fossil fuels have fueled the world economy for decades. However, given their limited na-
ture, fluctuating prices and the escalating environmental concerns, there is an urgent need to develop
and valorize cheaper, cleaner and sustainable alternative energy sources to curb these challenges. Bi-
omass represents a valid alternative to fossil fuels, especially for fuel and chemical production as it
represents the only natural organic renewable resource with vast abundance. A vast array of conver-
ARTICLE HISTORY sion technologies is used to process biomass from one form to another, to release energy, high-value
products or chemical intermediates. This paper extensively reviews the thermochemical processing
Received: July 22, 2019 of biomass to fuels and high-value chemicals, with an emphasis on the process performance, condi-
Revised: August 28, 2019
Accepted: October 05, 2019
tions, and weaknesses. Technologies with great future prospects as well as those with possible link-
age to CO2 capture and sequestration are highlighted. The important chemical compositions of bio-
DOI:
10.2174/2405463103666191022121648 mass feedstock, their conversion technologies and most importantly, the role of catalysis in their
conversion to fuels, fuel additives, based chemicals, and added-value chemicals are also discussed.
Special attention is given to biofuel production for transportation as this sector is responsible for the
highest global greenhouse gas emissions, and has an emerging market with promising future pro-
spects for sustainable large-scale biomass processing. The processes involved in the purification and
upgrading of biomass-derived products into higher-value products are equally discussed and re-
viewed.
Keywords: Biofuel, biomass processing, biomass, biorefinery, green chemistry, thermochemical routes.
1. INTRODUCTION resource, relatively cleanest and most abundant among the

renewable energy resources [3], and is regarded as one of the
Fossil fuels, the main source of global energy (81% of
most promising fossil fuel alternatives for energy, chemicals
the energy supply) satisfactorily meet the current energy and
and biofuels production [7, 8]. The negligible amounts of
chemical needs [1, 2], despite their environmental setbacks
nitrogen, sulphur, and ash in biomass make it a cleaner fuel
and other concerns. They are used mainly as fuels for trans-
compared to fossils due to its low SO2, NOx and soot emis-
portation or combusted in gas/thermal engines or power
sions. Zero net CO2 emissions can be achieved with biomass
plants for electricity production. The use of fossil fuels,
due to the quantitative recycling or sequestration of its CO2
however, leads to the emissions of greenhouse gases
released by plants during photosynthesis [9].
(GHGs). These emissions, together with their limited nature,
rapid depletion, price fluctuations, environmental concerns Also, the interest in the development and valorization of
(global warming or climate change), and the growing de- biomass as a source of fuel for the reduction of the environ-
mand for energy has led to the current strong drive, wide- mental concerns from energy generation and in the expan-
spread interest and investments in renewable energies [3-5]. sion of domestic and renewable energy sources for both rich-
Biomass energy is a sustainable substitute for fossil fuels er and poorer countries stems right from the 1970s energy
(oil, natural gas, and coal) in the provision of energy, fuels, crisis [10]. Apart from its direct energy production, there is
and chemicals [1, 6]. It is the only renewable organic currently a growing interest and attention to develop pro-
cesses capable of converting biomass to fuels (bio-oil, bio-
syngas, etc.) and vital industrial bio-based chemicals [7].
*Address correspondence to this author at the Pan African University, Insti-
tute of Water and Energy Sciences (including Climate Change), BP 119 Currently, biomass fuels (agricultural residues, wood, and
Tlemcen 13000, Algeria; Tel: 676565036; E-mail: [email protected] herbaceous materials) constitute the third largest primary
2405-4631/20 $65.00+.00 © 2020 Bentham Science Publishers

2 Current Alternative Energy, 2020, Vol. 4, No. 1 Muh et al.
energy resource worldwide. Their conventional conversion transport sector [1]. The development of new processes is
to energy is regarded as carbon neutral. However, the har- very crucial for the assurance of a smooth transition to re-
vesting of biomass for energy purposes seemingly may be newable carbon sources in the future. As such, pathways for
unsustainable as it depletes soil carbon and nutrients, leading the generation of bio-derived chemicals and alkanes required
to a reduction in soil productivity [5]. Recent studies [11] for the production of various transport fuels, chemicals and
indicate that roughly 3 billion people globally rely on tradi- materials are urgently needed. Alkanes (linear, branched and
tional biomass for heating, lighting, and cooking, resulting in cyclic), mainly obtained from fossils are vital chemical in-
the annual premature death of about 3.1 million due to intermediates and end products of the chemical industry, and
door pollution mainly in developing countries. In addition, biomass is an important alternative for the production of
about 2.7 billion people lack clean cooking facilities in sub- these chemicals and fuels [15]. Recent studies [16-18], has
Saharan Africa and Asia-Pacific, necessitating improved shown that several value-added chemicals (halocarbons, ar-
cooking facilities through biogas from anaerobic biomass omatics, alkanes, arenes, alkenes, ethers and epoxides, alco-
processing [12]. hols and phenols, carbonyls, and many other bifunctional
organic species), energy and transport fuels can be derived
The abundant and sustainable availability of biomass
directly from biomass or indirectly as biomass-derived in-
feedstocks is continuously being dominated and challenged
termediates via both thermochemical and biochemical path-
by biomass-derived wastes and residual materials with the
ways. However, more research is still required to optimize
inclusion of municipal solid waste, which when unprocessed
these processes to make them commercially viable for large-
causes serious problems [5]. The use of biomass wastes (ag-
scale applications. These processes will in the nearest future
ricultural, domestic, etc.) as bioenergy feedstocks compared
to energy crops, will among others reduce GHG emissions, become competitive with a continuous decrease in fossil
stress on land usage, as well as other associated impacts, supply and their rising costs. The transition to biomass-based
economy is presently being demonstrated by the current mul-
conflicts and ethical issues arising from food crops usages.
tidisciplinary drives towards the development of biorefiner-
This stands as a strong booster for bioenergy production and
ies that can successfully transform biomass to chemicals,
in the sustainability of biofuels and chemicals feedstocks
high-volume commodities, and platform molecules. This is
[13]. The optimal use and applications of renewable energy
challenged by the lack of novel separation, refinement and
resources and technologies can potentially minimize waste
transformation techniques that will maximize feedstocks
generations, enhance energy access and security, promote
conversion, thereby minimizing waste and promoting large-
sustainable development, and above all redress the current
scale applications [18].
environmental concerns associated with fossil use and de-
pendency [14]. This study presents a comprehensive review of the ther-
mochemical processes for biomass conversion to fuels,
Biomass energy resource is utilized in two ways: directly
chemicals, and vital material products, with special reference
through combustion and indirectly by transforming it into
to the concept of the biorefinery as well as recent develop-
solid, liquid and gaseous fuels or intermediate energy carri-
ments in this area. Considering the rapid progress so far in
ers [10]. A variety of techniques, categorized into biochemi-
biomass conversions into energy, this review concentrates
cal, thermochemical, biotechnological and physiochemical,
mainly on the available thermochemical routes of biomass
are currently being employed to convert biomass into various
transformations into fuels and value-added chemicals, with a
energy forms (heat, power, fuels, chemicals and other value-
special focus on the role of catalysis in these conversions.
added products) [3]. The thermochemical processes make
Recent developments and future prospects of these conver-
use of heat energy and chemical catalysts to decompose bi-
sion processes are also discussed. Details about reactors
omass into valuable energy-rich products, while the physical
methods use densification techniques that include crushing, technologies and designs are not covered in this review.
heat and pressure applications, to convert biomass into bio-
fuels. Also, the biochemical processes utilize naturally oc- 2. BIOMASS RESOURCE, CONSTITUENTS, AND
CHEMISTRY
curring micro-organisms and enzymes to process biomass
into desirable energy products. Biomass direct combustion 2.1. The Biomass Resources
primarily produces thermal energy, used for electricity pro-
Biomass is generally referred to any mixture of hydro-
duction, in combined heat and power (CHP) systems or re-
carbon material comprising carbon, hydrogen, and oxygen,
motely for cooking and heating especially in developing
with small amounts of nitrogen, sulphur and some minerals
countries. The indirect processing (gasification and pyroly-
[9, 10, 19]. This very important and versatile renewable re-
sis) gives rise to mainly liquid fuels (biofuels), chemicals,
source is an indirect source of solar energy and stores its
charcoal, electricity and CHP generations with internal com-
solar energy in the form of chemical energy via photosynthe-
bustion engines, turbines, and boilers. The liquefaction pro-
sis [14, 20]. Biomass covers a broad range of plant and plant-
cess (hydrothermal) directly converts biomass into crude oil
derived materials, including biodegradable wastes. It com-
for use as premium fuels after upgrading or for heat and
prises of all biological materials, including biological waste
power generation [10].
or dead biomass. They include: agricultural crops and resi-
Given that the required infrastructural developments for dues, forestry crops and residues, wood and wood wastes,
electric vehicles or hydrogen may last longer, biomass ener- sewage, municipal solid waste, industrial residues, animal
gy provides a huge potential for oil substitution in the residues, food processing wastes, dedicated crops and resi-
Biomass Conversion to Fuels and Value-added Chemicals Current Alternative Energy, 2020, Vol. 4, No. 1 3
dues, seaweeds, algae and aquatic plants [3-5], and these Biomass utilization is mainly challenged by its low ener-
biomass resources are divided into the following categories: gy density, inconvenient form, and bulkiness. As such, the
wastes, standing forests, agricultural residues, and energy handling, storage, and transportation of raw biomass are
crops and aquatic plants (algae, water weeds, water hyacinth, costlier compared to fossils. Therefore, to optimally and
reeds and rushes) [14, 21]. The energy crops include corn, fruitfully valorize biomass, an improvement of the biomass
sugar cane, grains, sorghum, sugar beets, elephant grass, properties that enhances its handling, storage and transport is
seaweeds (kelp) and many others. The choice of an energy very paramount. Biomass conversion technologies, therefore,
crop for energy production is dependent on the crop’s dry seek to elevate these properties and ameliorate these promi-
materials yield per unit of land (hectare). Higher yield reduc- nent setbacks of biomass utilization [6]. When compared to
es land requirements, thereby lowering the production cost of fossil fuels, biomass-derived fuels have low heating values
the biomass energy [10]. due to their high moisture and oxygen contents, low energy
density, high content of volatiles (about 80%), high ignition
Virgin biomass has vast global energy potential. The
world’s terrestrial standing biomass carbon is estimated to stability, high density due to the presence of oxygenates,
around a hundred times the total annual global energy con- acidic, corrosive and are very viscous [25].
sumption. Forest biomass comprises between 80% to 90% of
2.2. Biomass Chemistry and Conversion
the total biomass carbon. Marine biomass carbon (with least
natural abundance) is highly concentrated in oceanic and Biomass (terrestrial) consists mainly of the following
marshy land environments and is projected to precedes forest biological molecules: carbohydrates (sugars, cellulose, and
biomass carbon with respect to the net annual energy produc- hemicellulose), proteins, lignin and lipids (fatty acids, oils),
tion [22]. Biomass is the only renewable carbon source ca- extractives, starches, water, ash, hydrocarbons and other
pable of being converted into convenient solid, liquid and compounds [26, 27]. Lignin, cellulose, and hemicellulose
gaseous fuels, as well as added-value chemicals. Woody made up the bulk of a biomass species whereas sugars occu-
biomass is the oldest form of energy used by humans and is py less than 30% and lipids (oil) less than 10% of a bulk
applied traditionally in many parts of the world (especially in biomass species. Lignin and carbohydrates are usually re-
the poorer countries) through direct combustion for heating garded together as lignocellulose biomass [26]. Biomass
and cooking or indirectly through conversion into liquids or feedstocks vary greatly with respect to their chemical con-
gaseous fuels. However, biomass combustion produces pol- stituents and physicochemical properties, and these have a
lutants such as CO2 (the major component of greenhouse strong influence on their appropriate choice of conversion
gases), SO2 and NOx (both constituents of acid rain) and technologies [1]. Agricultural wastes are known to possess
dust. The amount of these pollutants released from biomass very high energy and chemical content as they have a higher
combustion is far less compared to that emitted from fossil composition of organic constituents like cellulose, hemicel-
combustion [21]. The majority of biomass energy is pro- lulose, lignin and trace amount of other organic compounds
duced from wood and wood wastes (64%), municipal solid or polymers [14].
wastes (24%), agricultural wastes (5%) and landfill gases
(5%) [10]. Biomass energy can be classified as traditional or The conversions of biomass vary and are dependent on
modern biomass. Traditional biomass includes fuelwood and the desired end products (energy, fuels or chemicals) and
charcoal, animal wastes, rice husk, and plant residues, used biomass streams available [13]. Whereas carbohydrates
in small scales in developing countries. Modern biomass (starches and sugars) are usually converted through biologi-
consists of wood and agricultural wastes, urban wastes, and cal fermentation into ethanol, lipids (fatty acids) are often
biofuels (biogas, energy crops, etc.) and they are involved in transformed into biodiesel through esterification (transesteri-
large-scale uses aimed at substituting for the conventional fication) with methanol or ethanol. The sugars from photo-
energy sources [21]. synthesis are usually metabolized into lipids, proteins, and
lignin. Cyclic carbohydrate (glucose) are often converted
The biomass resource can be processed into three major
into fatty acids with long-chain hydrocarbons having high
end products: transport fuels, chemical feedstock, and pow-
energy contents and excellent liquid properties [26]. Alterna-
er/heat generation through two principal conversion technol-
tively, solid biomass is often converted into synthetic gas
ogies: thermochemical and biochemical pathways. Among
(CO + H2), which is later transformed into liquid fuels and
the four thermochemical technologies, biomass gasification
other chemicals through the Fischer-Tropsch (FT) process,
has a great future prospect for renewable chemical produc-
requiring several complex steps, energy, and capital invest-
tion and for power generation via internal combustion en-
gines or turbines [23]. Good knowledge of the physicochem- ment. Direct liquefaction provides a simpler and more robust
ical properties of biomass is instrumental for its sustainable solid biomass to liquid (BTL) conversion. Several BTL
use for energy and chemical production. Parameters such as methods (thermal or thermocatalytic) are still under devel-
chemical composition, moisture content, the content of ashes opment [26].
and inorganic substances account for the diversity and dis- The choice of biomass as a source of energy depends on
parities among biomass species. The principal elements pre- its moisture content, calorific value, fixed carbon and vola-
sent in biomass in increasing order of abundance are: man- tile matter content, alkali metal content, ash, and residual
ganese, sodium, chlorine, iron, Sulphur, aluminum, magne- matter content, and the cellulose/lignin ratio [28]. The con-
sium, silicon, potassium, calcium, nitrogen, hydrogen, oxy- version of lignocellulosic biomass to fuels and chemicals is
gen and carbon [24]. often difficult, expensive and low-yielding due to the com-
Fig. (1). Processes for the pretreatments and conversions of lignocellulosic biomass [1]. (A higher resolution / colour version of this figure is
available in the electronic copy of the article).
plexities and the exact chemistry of the lignocellulose bio- other compounds are equally present and these components
mass polymers. Some of the processes available for the pro- are mainly found in the trunks, foliage, and barks of plants
cessing of lignocellulosic biomass, together with their prod- [10].
ucts and possible pretreatments steps are illustrated in Fig.
The distributions of the three major biomass constituents
(1) [1]. The worldwide distribution, vast abundance and the
are also species-dependent, with very prominent disparities
renewable nature of biomass have led to growing interest and
between hardwoods and softwoods. The deciduous woods
the devoted efforts currently employed for organic chemical
(hardwoods) have a relatively higher amount of cellulose,
production from various biomass streams, with particular hemicellulose, and extractives compared to the softwoods
focus on sugar conversions to value-added chemicals. The which only have a higher lignin content. Overall, hardwood
most suitable of the biomass sugar feedstocks used as chemi-
is made up of around 43-47% cellulose, 25-35% hemicellu-
cal precursors or intermediates are the hexoses, especially
loses, 16-24% lignin, and 2-8% extractives, whereas soft-
glucose and D-fructose [29].
wood is compose of about 40-44% cellulose, 25-29% hemi-
2.3. Biomass Composition cellulose, 25-31% lignin and 1-5% extractives [9, 27]. As
discussed by [28] and [30], biomass is composed of the fol-
Biomass is generally composed of organic and inorganic lowing major elemental composition on the dry mass basis:
constituents and a fraction of water [25]. The development of oxygen (30-40%), carbon (30-60%), and hydrogen (5-6%)
processes for the generation of fuels and chemicals from depending on the ash content. Sulphur, chlorine, and nitro-
biomass is strictly dependent on its chemical structure and gen make up less than 1% of the biomass. These elemental
the basic organic constituents [9]. Biomass is composed of composition in increasing order of abundance are: Al, Mg,
three main groups of naturally occurring polymeric materials Si, K, Ca, N, H, O, and C. The typical levels and description
on a dry mass basis. These are cellulose (about 50%), hemi- of the main biomass constituents are summarized in Table 1
cellulose (10-30% in woods and 10-40% in herbaceous bio- [25]. The major biomass organic constituents (cellulose,
mass), and lignin (20-40% in woods and 10-40% in herba- hemicelluloses, and lignin) and biomass elemental composi-
ceous biomass). It also consists of other constituents such as tion are characterized using the proximate and ultimate anal-
inorganic minerals compounds like the alkali metals com- ysis [31].
pounds (potassium, calcium, sodium, silicon, phosphorus,
Carbohydrates are polyhydroxy organic compounds gen-
magnesium and chlorine in herbaceous biomass) and extrac-
erally represented elementally as (CH2O)n. They have a uni-
tives (usually smaller organic molecules and polymers such
form carbon of about 40%, far less than in hydrocarbons.
as proteins, salts, and acids). However, the quantities of these
However, their oxygenated nature gives them superior phys-
inorganic compound vary from one biomass species to an-
icochemical properties that enhance their conversion and
other (wood (less than 1%), herbaceous biomass (15%), and
utilization. Carbohydrates are classified as monosaccharides,
25% in agricultural and forestry residues) [10]. Lipids, sim-
disaccharides and oligosaccharides, and polysaccharides.
ple sugars, proteins, water, starches, hydrocarbons, ash, and
Table 1. Basic levels and description of the main biomass organic constituents [25].
Component Percent Dry Weight (%) Description
High molecular weight (≥106) linear glucose chain linked by β-glycosidic bonds. The chain is stable
Cellulose 40-60
and resistant to chemical attack.
Highly branched short sugar chains (pentoses (D-xylose, L-arabinose) and hexoses (D-galactose, D-
Hemicellulose 20-40 glucose, and D-mannose) and uronic acid. They have lower molecular weight than cellulose and are
relatively easy to hydrolyzed into basic sugars.
A biopolymer rich in three-dimensional, highly branched polyphenolic constituents that provide plants
Lignin 10-25 structural integrity. Amorphous with no exact structure. More difficult to be dehydrated compared to
cellulose and hemicellulose.
First-generation biofuels feedstocks mainly comprise starch catalysts, waste material-based catalysts, have all been re-
and sugar, whereas cellulose and hemicellulose carbohy- ported in literature recently and their applications in lab-
drates constitute the second generation biofuels feedstocks scale biodiesel production. They are highly active, selective,
[1]. Cellulose and hemicellulose make up the carbohydrate and water-tolerant depending on the amount and strength of
portion of biomass, whereas the non-carbohydrate portion is the active acid or basic sites [33]. However, the role of het-
composed of lignin [28, 30]. erogeneous catalysts in the production of biodiesel and bio-
ethanol is limited due to their production pathways (bacterial
2.4. Catalysis in Biomass Conversion fermentation and transesterification using homogeneous ba-
ses). Heterogeneous catalysis is vastly applicable in the pro-
Organic catalysis (enzymatic catalysis) has traditionally duction of advanced biofuels (high energy density and infra-
been used in biomass processing. However, inorganic cataly- structural compatibility). This involved some relevant cata-
sis used in the conversion of raw biomass feedstocks to valu- lytic routes like pyrolysis/gasification accompanied by cata-
able products is to some extent more economically perfor- lytic upgrading, aqueous-phase processing of sugars and
mant [26]. Acid catalysis is widely applicable in biomass platform molecules, and hydrotreating of vegetable oils and
valorization owing to their superior ability towards molecu- related feedstocks [2].
lar deoxygenation through multiple chemical reactions [18].
Catalysts play a key role in biomass processing either in Catalysts also play a fundamental role in the gasification
promoting the conversion processes or in the upgrading of products. They improve the gas quality, conversion efficien-
the conversion products (liquids or gases) into high-value cy and reduce the tar content. Dolomite, alkaline metal ox-
fuels or chemicals. However, their nature and action vary, ides and Ni-based oxides are widely used gasification cata-
depending on the conversion of technology being used. lysts. Iron, cobalt, ruthenium and potassium-based catalysts
are well known for their role in the FT synthesis of diesel,
Heterogeneous catalysts play a central role in fossils con- hydrocarbons and other liquid fuels from bio-syngas. How-
version to fuels, power, and chemicals. However, their role ever, the performance of these catalysts varies and their
in biomass processing is still unclear, given the diametrically choice is determined by their properties, reaction pathways
opposing chemical nature of both resources. Zeolites over and the desired end product [34]. Recently, catalysis has
the past years have shown great potential for use in biomass become one of the principal processes required for the
valorization, especially in the conversion of lignocellulosic achievement of sustainable chemicals and energy production.
biomass to fuels and chemicals. They play a key role in the This is evident from the production of furan derivatives in
conversion of oxygenates to hydrocarbons, catalyzing reac- the past decades from biomass sugar, used as substitutes for
tions like dehydration, esterifications, decarboxylation, and oil-derived chemicals or as starting materials for new prod-
acylation. Thus, the use of zeolite catalysts in biomass pro- uct synthesis like vital polymeric materials, pharmaceutical
cessing is found to be a promising alternative method for the agents (fungicides), liquid fuels or solvents, macrocyclic
production of transport fuels and chemicals [32]. However, ligands [8, 29].
the design of novel catalytic routes for the selective, effi-
cient, and direct conversion of biomass feedstocks for the Despite the great and intriguing progress made in the cat-
production of targeted chemicals is a major challenge in the alytic transformation of biomass sugars into essential chemi-
field of biochemicals [2]. The transesterification process for cals and chemical precursors, there is still an urgent need for
biodiesel production is usually catalyzed by both homogene- further research to enhance the selectivities of the catalysts
ous and heterogeneous catalysts. and to improve their conversion efficiencies in order to fully
commercialize those processes. Also, further catalytic pro-
Heterogeneous catalysts (acid or base) like alkali metal gress for biomass processing should be focused on the rapid,
oxides and derivatives, transition metal oxides and deriva- economical and environmentally benign production of or-
tives, alkali earth metal oxides and derivatives, mixed metal ganic chemicals with recent developments and the concepts
oxides and derivatives, sulfated oxides, ion exchange resins, of green chemistry. In addition, priorities in catalytic chemis-
carbon-based catalysts, enzyme base catalysts, boron-based try should be given to multi-purpose catalysts originating
Table 2. Classification of biofuels [3, 19].
Biofuel type Description Examples
• Bioethanol from sugar cane, sugar beet and starch crops (corn and wheat)
Produced from raw materials compet- • Biodiesel from oil-based crops (rapeseed sunflower, soyabean, palm oil, and
First generation biofuels
ing with the food and feed industry waste edible oils
• Starch-derived biogas
• Biogas from waste and residues

Produced from non-food crops (energy
Second-generation biofuels • Biofuels from lignocellulosic materials
crops), or waste residues
• Biofuels from energy crops
Produced from aquatic micro- • Algal biodiesel

Third-generation biofuels
organisms like algae • Algal hydrogen
Biofuels based on high solar efficiency • Carbon-negative technology

Fourth-generation biofuels
cultivation • Technology of the future
from the incorporation of transition metals with acid/base and chemicals. These are the biochemical, thermochemical
solid catalysts. This will permit several reaction steps to be and physiochemical processes. The biochemical pathway
conducted in a single reactor, avoiding the costly intermedi- consists of two main processes (anaerobic digestion and fer-
ate separation processes. Moreover, catalysts recycling and mentation), the thermochemical pathway consists of four
the efficient recovery and separation of the targeted products major processing options (combustion, gasification, pyroly-
are also very instrumental in biomass catalytic conversion sis, and liquefaction) and the physiochemical route mainly
and in catalytic studies as a whole. However, these are chal- consists of extraction, followed by esterification, whereby
lenged due to lack of perfect understanding of the catalysts oils are obtained from the crushing of oilseeds [13].
structure-property relationships and exact biomass conver- Through these conversion processes, biomass can be
sion reaction mechanisms, multi-purpose catalysts and their used to produce different forms of energy (heat, electrical,
suitable solvent systems, process compositions, catalyst op- chemical energy or fuels). Its energy density is often upgrad-
timization, and development, especially for large-scale pro- ed through the production of fuels such as liquid fuels
duction systems [29]. (transport fuels), charcoal, gaseous fuels (H2, biogas, pro-
ducer gas). The bioconversion processes of biomass mainly
3. BIOMASS CONVERSION TECHNOLOGIES give rise to biofuels (bio-alcohols, bio-dimethyl ether, syn-
3.1. Overview of Biomass Conversion Processes thetic natural gas (bio-methane), Fischer-Tropsch fuels, and
hydrogen), broadly classified into four groups (Table 2) de-
Biomass conversion processes mainly achieved two pending on the biomass feedstock used [3, 19]. Biomass is
goals: energy production and environmental clean-up. Two mainly utilized through combustion for heat and power gen-
major pathways are used for biomass processing: the biolog- eration, conversion into gas-like fuels (CH4, H2, and CO), or
ical (biochemical) and the thermochemical pathways. The conversion into liquid fuels (biofuels). Presently, biomass
thermochemical pathways usually have higher efficiencies energy contributes about 14% of the total global energy con-
than the biological processes due to their low reaction times sumption, compared to 12% from coal, 15% from gas and
and superior ability to destroy the organic constituents of 14% from electricity [27].
biomass [25, 28]. The feedstocks for biomass conversion can
be highly variable in terms of mass and energy density, The first-generation biofuels, with commercialized tech-
moisture content, size, and intermittent supply. As such, nologies, are primarily produced with food or feed raw mate-
modern industrial technologies are often hybridized with rial feedstock like simple sugars, fats, starch, and vegetable
fossil fuel such that in case of biomass supply irregularities, oils. The controversy of food versus energy lead to the de-
the fossil fuel is used for preheating, drying and in the velopment of second-generation biofuels, produced mainly
maintenance of fuel supply [22]. from lignocellulose biomass such as non-feed crops, forest
residues, domestic, agricultural and industrial wastes. Alt-
The pathways for biomass conversion into various energy hough the second-generation biofuels overcame the contro-
forms vary. The choice of an appropriate conversion process versial food versus fuel challenge of the first-generation bio-
depends on the biomass quantity, type, desired energy or fuels, they still require vast arable land to cultivate the feed-
chemical end product, the feedstock characteristics, econom- stock crops. Thus, depriving food cultivation and indirectly
ic conditions, policy and environmental standards [13]. imposing the same controversy with the first-generation bio-
Among these, the dominant factors are the desired energy fuels. These issues are addressed with the third-generation
form and feedstock availability. Three principal process biofuels that use algae and seaweeds which are grown on
technologies govern biomass conversion into energy, fuels, unproductive land, marshy land, and sea waters. These tech-
nologies are still under development. The fourth-generation fication or liquefaction and directly as heat through combus-
biofuel technologies are still at the conceptual stage. They tion and/or co-firing. The most valuable of these technolo-
are intended to be produced by technologies that will suc- gies are those with liquid or gaseous intermediate energy
cessfully transform biomass into fuel in a way that the CO2 carriers with higher potentials of upgrading to more energet-
consumed in their generation is larger than that produced ic molecules or fuels [13, 36]. Among these processes, gasi-
during their use or combustion. As such, these biofuels fication is the most efficient and cost-effective for bio-
would be very vital in mitigating climate change through the energy generation from lignocellulose biomass [19]. These
reduction of atmospheric GHGs. They result from genetical- processes occur by varying their operating conditions, name-
ly engineered algae, a carbon-negative energy resource, with ly heating rate, vapor residence time, reactor configuration,
enhancing hydrocarbon yields, giving rise to an artificial etc. The pyrolysis solid product (biochar) is highly applica-
carbon sink [3, 19]. ble in the sequestration of carbon through soil management
systems. The gasification process mainly generates flue gas,
The second-generation biofuels are mainly produced via
together with syngas which is the feedstock for the produc-
biochemical and thermochemical methods from lignocellulo-
tion of synthetic liquid fuels via the FT synthesis or burnt for
sic materials. Thermochemically, the process consists of
heat and power generation [10]. The liquefaction process
gasification and/or pyrolysis, followed by the processes for
(hydrothermal) focuses only on liquid fuels production under
gas cleaning and conditioning and finally the FT synthesis to
high pressures in various solvents like water, acetone, meth-
generate synthetic liquid fuels. Biochemically, the cellulose
anol or their mixtures [31]. The stages, processes, and prod-
and hemicellulose components of biomass are first broken
ucts involved in biomass thermochemical transformations
down enzymatically into their constituent sugars, which are
then fermented to bioethanol. This pathway is less prone to are illustrated in Fig. (2) [13], and their characteristics are
commercialization than the former but shows great future summarized in [13, 36].
cost reduction potentials [35]. Whereas the thermochemical The thermal depolymerization and decomposition of the
processes occur at higher efficiencies with short reaction structural constituents of biomass (cellulose, hemicellulose,
times and have the ability to completely decompose vast and lignin) give rise to chemicals in the form of liquids, gas-
organic compounds in biomass, the biological processing es, together with residual solid charcoal. Pyrolysis oil com-
shows low efficiencies with higher reaction times (days, prises of an array of chemicals such as cyclopentanone,
weeks, etc.) and is unable to completely breakdown most methanol (most valuable), methoxyphenol, acetone, acetic
organic compounds in biomass such as lignin [13]. The next acid, phenol, levoglucosan, furfural, guaiacol and their alkyl-
sub-sections of this paper present an overview of the current ated phenol derivatives, and formic acid. The composition of
biomass thermochemical conversion routes for fuels and these chemicals is mostly depended on the process heating
chemical production - pyrolysis, gasification, and hydro- rate and temperature. Lignin conversions gives rise to chem-
thermal processing (precisely hydrothermal liquefaction). ical like syngas, methanol, dimethyl ether, ethanol, mixed
alcohols, C1-C4 gases, hydrocarbons, Fischer-Tropsch liq-
3.2. The Thermochemical Conversion Pathways uids, styrenes, oxygenates, phenol, cyclohexane, biphenyls,
They are commonly used to convert biomass into higher substituted phenols, cresols, catechols, eugenols, resorcinols,
heating value fuels, reducing the biomass oxygen content to syrinols, guaiacols, vanillin, vanillic acid, aromatic acids,
increase their energy density as well as increasing the weight aliphatic acids, quinones, syringaldehydes, aldehydes, cyclo-
of the final hydrocarbon fuel via the creation of carbon- hexanal, beta keto adipate, cyclohexanol/al, toluene, ben-
carbon bonds [19]. These processes do not solely produce zene, xylene and derivatives, higher alkylates, substituted
useful energy from biomass directly, but also convert bio- lignins, drugs, mixed aromatic polyols, carbon fiber, fillers,
mass into more convenient, easily transportable and more and so on [27].
energy-dense forms of energy carrier (producer gas, oils,
alcohols, etc.) under controlled temperatures and oxygen 3.2.1. Pyrolysis
condition [22]. They are dependent on the biomass feedstock Pyrolysis refers to the thermal breakdown of biomass
type, physicochemical properties, and the process operating (mainly lignocellulosic biomass) to liquid (tar or bio-oil),
conditions and these affect process conversion time, product carbon-rich solid (char or biochar) and a mixture of non-
distribution and quality [10]. The products of biomass ther- condensable gases in the absence of oxygen at elevated tem-
mochemical processing are usually classified as a carbon- peratures [25]. Gases results when the process temperatures
rich residual fraction and the volatile fraction (gases, vapor, are high with longer residence times, and longer vapor (hot)
and tar) [9], and are generally in the form of solid, liquid and residence times. Lower process temperatures favor charcoal
gaseous fuels with equal ecological and industrial im- production whereas short vapor residence times and lower
portance [14]. temperatures are best for liquid production. The proportion
The thermochemical processing of biomass occurs via of these three key products produced during a pyrolysis pro-
combustion, gasification, pyrolysis, carbonization, and lique- cess is dependent on the process condition or how the pro-
faction processes, with pyrolysis being a preliminary stage in cess conditions are varied [13]. This process generates fuels
all the processes. These processes release the energy content with high fuel-to-feed ratios, and this makes it the most effi-
of biomass by transforming it into solid (charcoal), liquids cient biomass conversion route. In addition, the optimization
(bio-oils) or gaseous fuels (synthetic gas) via pyrolysis, gasi- of the high-value fuel products via thermal and catalytic
Fig. (2). Biomass thermochemical conversion pathways [13]. (A higher resolution / colour version of this figure is available in the electronic
copy of the article).
Table 3. Biomass pyrolysis modes, process conditions, and product distribution [13].
Product Distribution
Mode Conditions
Liquid (wt.%) Solid (wt.%) Gas (wt.%)
Fast ̴ 500°C. Shot hot vapor residence time ˂2s 75 12 13
Intermediate ̴ 500°C. Moderate hot vapour residence time 5-30s 50 (2 phases) 25 25
Carbonization (slow) ̴ 400°C. Long hot vapour residence time (hours to days) 30 (2 phases) 35 35
Gasification (allothermal) ̴ 750-900°C. Moderate hot vapour time >5s 3 1 96
0, unless vapours are con-

Torrefaction (slow) ̴ 280°C. Solid residence time, ̴ 10-60mins 80 20
densed, then up to 15%
pathways is the main objective of this process [9]. In a nut- temperatures, ranging from 400-700°C, and are found to be
shell, pyrolysis offers a broader perspective and opportuni- much lower in biomass species containing metallic com-
ties for biomass valorization than the other thermochemical pounds. Also, it occurs at lower pressures (0.1-0.5 MPa)
conversion processes and is broadly classified into two compared to higher pressures ranging from 10 MPa to 25
groups (fast and slow) depending on the operating conditions MPa with hydrothermal liquefaction [10]. Temperature is a
[10]. Pyrolysis plays a fundamental role in reactors design, major determinant for the distribution of pyrolysis products.
reaction kinetics, and in the determination of product distri- The products are mainly produced between 352°C-452°C. At
bution, properties, and composition, in all the viable thermo- higher temperatures, the gaseous fraction is enriched with
chemical biomass conversion processes [9]. lighter molecules through the breakdown of heavier mole-
cules found in the liquid and residual solid. High liquid pro-
Generally, four key pathways generate transport fuels via
duction arises at high temperatures, high heating rate and
pyrolysis: slow pyrolysis and syngas upgrading, fast pyroly-
short residence time, while high residence time, low heating
sis and hydroprocessing, catalytic pyrolysis and hydropro-
rate and low temperatures favor char production. Increasing
cessing, and hydropyrolysis and hydroprocessing [37]. Hy-
temperatures reduces charcoal yield. The fuel gases are pro-
droprocessing refers to the integrated hydrocracking and
duced under high temperatures, long gas residence time and
hydrotreating processes. The feedstock chemical composi-
high heating rate [9].
tion and the process temperature strictly determine the quan-
tity, types, and quality of the resulting products [14]. Table 3 Heat is usually provided externally to thermally crack the
highlights the various types of pyrolysis, process conditions, biomass constituents into gases and vapor, which through
and product distribution [13]. The end products of pyrolysis secondary reactions give rise to the broad product spectrum
originate both from the primary breakdown of the solid bio- [13]. A number of factors affect biomass pyrolysis perfor-
mass species and the secondary reactions of the condensable mance, product types, distribution, and quality. These in-
volatile organic products into char, lightweight gases, and clude: feedstock type, temperature and heating rate, volatiles
secondary tar. Contrary to combustion and gasification that residence time and pressure, particle size, shape and orienta-
occur at higher temperatures, pyrolysis is conducted at lower tion, reactor configuration, catalysts, additives, and physico-
chemical properties such as thermal conductivity and emis- As fast pyrolysis for liquids occurs in few seconds, mass
sivity, permeability and density, specific heat capacity and and heat transfer processes, reaction kinetics and phase tran-
heat of reaction, particle shrinkage and moisture content, and sition phenomena play a major role. Thus, bringing the react-
the external heat transfer coefficient. The outcome of any ing biomass particles quickly to the optimum process tem-
pyrolysis process, therefore, depends on how these parame- perature and minimizing their exposure to lower tempera-
ters are varied [10]. The much interest in pyrolysis arises tures (charcoal production) and higher temperatures (thermal
from its operational flexibility, technology versatility, and its cracking) is very important in this process [13]. This is main-
adaptability to a wide range of biomass streams and products ly achieved in fluidized bed reactors. The reactor commonly
[13]. used for fast pyrolysis includes bubbling fluidized-bed, cir-
culating fluidized-bed, ablative flow, entrained flow, rotating
Fast pyrolysis (thermolysis) operates under moderate
cone and vacuum reactors [25].
temperatures of about 500°C and is characterized by high
heating rate, short hot vapor residence time (˂2s), and over- Fast pyrolysis is also reported to produce hydrogen gas at
all short reaction time. Here, the biomass is broken down elevated temperatures (700-100°C), through steam reforming
swiftly to mainly vapor and aerosols, with some charcoal and and water-gas shift reactions. These reactions mainly convert
gas. Thereafter, the vapor is cooled and condensed into a methane, simple aromatics, other hydrocarbon vapors (C2-
dark brown homogeneous liquid [13]. It favors the produc- C5), and others, into hydrogen. Overall, steam reforming
tion of liquid products but inhibits solid char formation [25]. converts the hydrocarbons into CO and H2, and the CO then
Its feedstocks generally have small particle size, with a pro- combines with H2O to produce H2 and CO2 via the water-gas
vision in the system for the rapid removal of the vapor to shift reactions [25]. It is a commercialize technology for
prevent further contact with the hot solid particles. The reac- chemical production but is still under development for the
tor systems for fast pyrolysis include: fluidized bed, ablative production of liquid fuels. Compared to the other thermo-
systems, vacuum pyrolysis systems and the stirred or moving chemical conversion processes, small scale fast pyrolysis
beds reactors [10]. Fast pyrolysis is currently of great com- processes have higher energy efficiencies and relatively low
mercial interest as it gives rise to liquids which can be investment costs [9].
stored, transported, used as energy, efficient energy carriers,
Slow and intermediate pyrolysis focus on the production
chemicals, fuel precursors and transport fuels. It produces
of solid char with liquids and gases as by-products. Slow
about 60-70wt.% of liquid bio-oil, 15-25wt.% of solid char,
pyrolysis occurs under gentle heating at low temperatures
and about 10-20wt.% of non-condensable gases. To maxim-
with longer vapor residence times and larger particle sizes. It
ize liquid production, the process is kept under low tempera- is a well-known process that occurs between 277-677°C and
ture, high heating rate and short gas residence time and to often appears in the traditional charcoal kiln [14]. The agitat-
maximize gas production, high temperature, long residence
ed drum kilns, large retorts (continuous or batch), rotary
time and the low heating rate is required [9]. However, with
kilns and screw pyrolyzers are commonly used slow pyroly-
rapid heating and quenching rates, intermediate pyrolysis
sis systems [10]. Slow pyrolysis has often been used to re-
liquid results which condense prior to the further decomposi-
duce the harmful effects of waste on the environment as well
tion of its higher weight constituents into gaseous products
as reduces waste quantities for disposal. Also, pyrolysis has
[9], [14]. The key features of fast pyrolysis for liquid produc-
been used for centuries for the production of charcoal, until
tions (high yields) are [9, 13, 14, 25]:
recently (last 35 years) that fast pyrolysis for liquid produc-
tion was developed [13]. The flash pyrolysis process oper-
• Particle size of less than 5mm for fast devolatiliza-
ates at temperatures within 777-1027°C to produce the petro-
tion and high heating rates.
leum equivalent of bio-oil of up to 70% yield efficiency.
• Short vapor residence time (˂2s) to minimize sec- This process also gives rise to pyrolytic water, posing major
ondary reactions. setbacks to this process. This bio-crude oil can be used di-
rectly as fuels in boilers, engines, and turbines or as refined
• A controlled reaction temperature of around 500°C
fuels for heat and power generation [14].
to maximize liquid yields.
• Feedstock moisture content of less than 10 wt.% as 3.2.1.1. Pyrolysis Products and Uses
all the feed in water settle in the liquid phase togeth- Biomass pyrolysis is a very prominent pathway for the
er with water from the pyrolysis reactions. generation of solid (char), liquid (tar) and gaseous products
• Very high heating and heat transfer rates at the bio- which are potential alternative energy sources or substitute
mass particle reaction interface. This requires a fine- for petroleum fuels. The liquids may be used directly as liq-
ly ground biomass fed of less than 3mm due to its uid fuels for boiler, diesel engine, and gas turbine for heat
low thermal conductivity. The particle heating rate is and power production added to the feedstock of the petrole-
the rate-limiting step in this process. um refinery or catalytically upgraded into liquid transport
fuels. Other applications may require its alkalis content to be
• Rapid char removal to minimize vapor cracking. removed and oxygen content lowered via catalytic cracking
• Rapid cooling of pyrolysis vapor and aerosols to and hydrogenation [9, 14]. It mainly gives rise to a carbon-
produce bio-oil. rich solid and volatile matter or flue gas. The flue gas is gen-
erally used as solvents (acetone, methanol), hydrocarbons
Table 4. Chemical constituents of fast pyrolysis liquid [9].
Major Components Mass %
Water 20-30
Lignin fragments: insoluble pyrolytic lignin 15-30
Aldehydes: formaldehyde, acetaldehyde, hydroxyacetaldehyde, glyoxal, methylglyoxal 10-20
Carboxylic acids: formic acid, propionic acid, butyric, pentanoic, hexanoic, glycolic (hydroxy acetic) 10-15
Carbohydrates: cellobiosan, α-β-levoglucosan, oligosaccharides, 1,6-anhydroglucofuranose 5-10
Phenols: phenol, cresols, guaiacols, syringols 2-5
Furfurals 1-4
Alcohols: methanol, ethanol 2-5
Ketones: acetol (1-hydroxy-2-propanone), cyclopentanone 1-5
and electricity productions. The bio-oil component is a major for conventional diesel fuel due to their oxygenated nature
source of chemicals like acetic acid and levoglucosan, which and water content. Their moderately acidic nature (pH range
can be upgraded into motor fuel or combusted for electricity 2.5-3.0) contributes to the corrosive nature of the oils. Also,
generation. The produced char could either be used as slurry the kinetic viscosities and densities of oxygenated bio-oils
fuel, soil enrichment agent or used as activated carbon in are much higher than their petroleum counterparts [9].
industrial applications [10]. Pyrolysis plays a fundamental
Bio-oils are generally used as fuels in engines, boilers,
role in reaction kinetics, reactor design and in the determina-
turbines, and CHP plants for heat and power generation, up-
tion of product distribution, composition and properties in all
graded through thermal or catalytic cracking into transport
the thermochemical conversion processes [14].
fuels or can be used for the synthesis of valuable chemicals
The pyrolysis liquids are dark brown viscous oils with and organic solvents. However, bio-oils applications are so
well-known chemistry and no exact precision on their exact far limited by their poor volatility, high viscosity, corrosive-
quantitative constituents. They are mainly composed of ke- ness, and coking. The range of chemicals that can be derived
tones, aldehydes, organic acids, phenols, anhydrosugars like from the fast pyrolysis oils, their minimum, and maximum
levoglucosan, pyrolytic lignin (guaiacyl- and a syringyl- weights are found in study [9] and it covers the following
based fragment of the original polymeric lignin), and a sig- chemical groups: organic acids, ketones, alcohols, aldehydes,
nificant amount of water (about 25%). The pyrolysis liquid esters, sugars, oxygenates, phenolics, hydrocarbons, and
consists of two distinct phases: the aqueous phase (higher steroids. These consist of a range of compounds like cyclo-
methanol, acetic acid, and acetone ratios) comprising a broad pentanone, acetic acid, methoxyphenol, methanol, acetone,
range of low molecular weight organo-oxygen compounds, phenol, levoglucosan, furfural, formic acid, guaiocol, and
and a non-aqueous phase (tar or bio-oil) of high molecular their alkylated phenol derivatives.
weight insoluble organics (aromatics) [9]. Table 4 shows the
chemical composition of fast pyrolysis liquids [9]. 3.2.1.2. Catalytic Pyrolysis
The bio-oil fraction of the pyrolysis products is a liquid This occurs in the absence of air under moderate temper-
mixture of oxygenated compounds that contains the carbox- atures (about 500°C), high heating rate, and short residence
yl, carbonyl, and phenolic groups. Its composition varies time, to produce mainly liquid, used as a source of fuel or
greatly from the petroleum-derived fuels and chemical, but valuable chemicals. This is the most attractive approach to
are very similar to that of the original biomass, thereby pos- minimize the polymerization, corrosivity, low thermal stabil-
ing a major challenge to these pyrolytic oils or in its possibil- ity and high viscosity challenges associated with the liquid
ities in substituting fossil-derived fuels. Bio-oil is made up of pyrolysis products, as well as facilitates the handling and
about 20-25% water, 25-30% water-insoluble pyrolytic lig- treatments of these liquid products [9]. Cracking reactions
nin, 5-12% organic acids, 5-10% anhydrosugars, 5-10% non- and the upgrading of biomass products are the influence of
polar hydrocarbons, and 10-25% of other oxygenated com- catalyst during a pyrolysis process, with strict dependence on
pounds. The low energy density of bio-oils is attributed to the catalyst type and reactor configuration. Various liquids
their water content, which reduces the oils flame tempera- and gaseous fuels arise from the catalytic cracking of pyroly-
tures, causes ignition difficulties, possible injection difficul- sis vapor over different catalysts. Zeolites catalysts are par-
ties and premature evaporation of the oil when preheating. ticularly useful in the reduction of oxygenates (which de-
They are very polar and readily absorb over 35% water, con- creases the energy content) of the specific pyrolysis oil [10].
trary to the non-polar and insoluble petroleum oils. They also Catalysts are mainly used to facilitate the cracking of heavier
have a low heating value of 16 MJ/kg compared to 43 MJ/kg molecules in bio-oil to lighter ones, giving rise to a less vis-
Table 5. Properties comparison between diesel fuel and pyrolysis oil (40°C and 25% water) [32].
Physical Properties Pyrolysis Oil Diesel Fuel
Moisture content 20-30wt% 0.1wt%
pH 2.0-2.5 -
Density 1.2kgL-1 0.94kgL-1
Elemental analysis (wt%)
C 55-58 85
H 5-7 11
O 35-40 1
N 0-0.2 0.3
Ash 0-0.2 0.1
HHV as produced 16-19 MJkg-1 40 MJkg-1
Viscosity 40-100 cp 180 cp
Solids (char) (wt%) 0.1-0.5 1.0
Vacuum distillation residue Up to 50 wt% 1 wt%
cous oil, less corrosive bio-oil (by reducing the synthesis of product upgradation [9]. The upgrading of bio-oil to quality
carboxylic acids), and lastly to promote the synthesis of transport fuels is done through the following three principal
high-value products (hydrocarbons) capable of raising the routes: hydrodeoxygenation with a hydrotreating catalyst
heating value of bio-oil [9]. Catalysts modify the pyrolysis (alumina supported sulphided CoMo or NiMo), zeolite up-
process as follows [10]: grading and emulsions formation with diesel fuel. Also,
steam reforming can be used to concert char and bio-oil into
• May cause a remarkable decrease in the breakdown
syngas or H2 [9]. Bio-oil is often produced with impurities
temperatures of biomass constituents.
and therefore needs to be upgraded to enhance its quality and
• Affects reaction networks (deoxygenation), as well purity. This can be done either physically, chemically or
as reduces polymerization precursors (multifunction- catalytically [13].
al phenols) for stabilizing bio-oil.
The catalytic bio-oil upgrading consists of the full deox-
• May lead to the release of CO, CO2, and H2O during ygenation of bio-oil and conventional refining, achieved ei-
decarboxylation, decarbonization and dehydration ther by integrated catalytic pyrolysis or decoupled liquid
reactions. phase hydrodeoxygenation. The partial upgrading into inter-
mediate products compatible with refinery streams is also
• Promote coke formation via dehydration reactions
envisaged to exploit the benefit of the economy of scale and
(arises mainly from catalysts high acidity).
the broad experience in the conventional refinery. The main
upgrading methods through refineries integration are hydro-
3.2.1.3. Bio-oil Upgrading to Fuels and Chemicals
deoxygenation, catalytic vapor cracking (in-situ or ex-situ)
Biomass-derived bio-oil in its unprocessed form has very and gasification to syngas followed by the synthesis of alco-
high moisture content, low energy density, and no free- hols or hydrocarbons [13].
flowing physical form, making it unsuitable for direct use in Hydrodeoxygenation involves the treatment of bio-oil
engines. Therefore, these necessitated the need for bio-oil with high-pressure hydrogen at moderate temperatures
cleaning and upgrading, to enhance its energy density, fuel (302°C-602°C) in the presence of heterogeneous catalysts to
properties and remove any impurities present [38]. Table 5 form saturated C-C bonds via oxygen removal, raising the
highlights the distinct characteristics of pyrolysis oil com- fuel energy content and stability. Sulphided CoMo/Al2O3
pared to diesel fuel [32]. and NiMo/Al2O3 are often used to hydrotreat industrial feed-
Bio-oil is generally known for its viscosity, acidity, stocks [9]. This requires a source of hydrogen, moderate
thermal instability, and its high constituent oxygenated com- temperature of about 400°C and high pressure of about 20
pounds. The production of a high-quality bio-oil capable of MPa. Complete deoxygenation is often challenging due to
substituting fossil fuels perfectly is often very challenging. the presence of phenols in bio-oil. Full hydrodeoxygenation
To overcome this challenge, the bio-oil quality needs to be produces a naphtha-like product, requiring conventional re-
enhanced either at source before full production or via the fining to derived conventional transport fuels such as gaso-
line, diesel, methane, LPG, and kerosene. The naphtha syngas and/or bio-oil to potential biofuels and chemicals
equivalent yield from biomass without hydrogen provision is [19]. Biomass gasification is a well-known technology that
projected to about 55% in terms of energy or 25wt.%. With produces mainly gaseous products at high temperatures
the inclusion of hydrogen from biomass gasification reduces through the partial oxidation of biomass, alongside a small
the yields to about 33% in terms of energy and 15wt.% [13]. amount of tar and ash. The gas production is optimized at
The hydrogen supply should be renewable and sustainable. higher temperatures and the process is often classified based
This can be done through biomass gasification, CO shifting on the gasifying agent: steam, air, air-stream, steam-oxygen,
to H2 followed by CO2 scrubbing, or steam-reforming to H2 oxygen-enriched air, etc [34]. Advanced gasification pro-
of bio-oil or the aqueous phase from a phase-separated prod- cesses, such as plasma gasification and the supercritical wa-
uct or H2 locally generated through the electrolysis of water. ter gasification have recently been employed for the decom-
External H2 supply is unlikely due to high transport and stor- position of biomass into mainly H2, as well as CO and CO2
age costs [13]. for the plasma gasification process [6, 13, 25].
Zeolite cracking/upgrading takes place under atmospher- Biomass gasification occurs in gasifiers which vary based
ic pressure at temperatures within 352°C-502°C in a closed on their hydrodynamics (precisely the manner of contact
process coupled to pyrolysis and removes oxygen mainly as between the gasifying agent and solid fuel), operating condi-
CO2 with race amount of CO due to catalyst coking. This tions (temperature, pressure, etc.), and the gasifying agents
improves the thermal stability of the oil. The process yield is (air, oxygen or steam). The most common types of gasifiers
projected to around 18wt.% aromatics. The production of are fixed-bed (updraft, downdraft or cross draft) gasifiers,
aromatics, a very important base chemical through this pro- fluidized-bed gasifiers, and the entrained flow gasifier.
cess is of great significance to the chemical industry [13]. Among these gasifiers, the most suitable are the fixed-bed
Due to the undesirable effects of pyrolysis oil that disfavors gasifiers [6, 25, 34, 35]. The designs of these gasifiers, how-
its direct use, the oil is often upgraded via conversion into ever, depend on the energy requirement, fuel type and char-
gasoline using zeolites (crystalline microporous alumino- acteristics (moisture, particle size, density, ash content, and
silicate materials). In this process, the oil vapors are passed toxicity), nature of oxygen injection and the combustion bed
through the catalyst between 300°C-500°C to produce hy- type [14, 19]. The supercritical water gasification (SCWG) is
drocarbons and by-products like H2O, COx, and coke. Coke a highly efficient gasification pathway for H2 (with low tar)
formation (on the zeolites) eliminates the coking effects of production from high moisture biomass species like algae,
the unprocessed bio-oil. The catalyst removes the oxygen manure, olive mill water, sludge, etc. [19]. In this sub-
content of the oil in the form of water, CO2, and CO, depend- section, design details, operation principles, performance
ing on the class of organic compound involved [32]. Zeolite characteristics and comparisons of biomass gasifiers are not
cracking of bio-oil is highly beneficial in that there is no included or discussed. However, the gasification process,
requirement for H2, takes place under atmospheric pressure product transformations, purification, and upgrading are
and this greatly reduces the operating cost, and the process highlighted and deeply discussed.
occurs under similar temperature to those for the production
of bio-oil. The ZSM-5 zeolite catalysts with strong acidity, 3.2.2.1. Principles of Biomass Gasification
high activities and shape selectivities convert oxygenated oil
This process converts organic feedstocks (solid fuel or
to hydrocarbon mixture ranging from C1 to C10. The major
liquid) into gases depending on the process temperature.
drawbacks to this process include easy coking, low yield
Syngas is primarily produced at extremely higher tempera-
(14-22.5%), and short catalyst lifespan [9].
tures (>1200°C) and at lower temperatures, a gaseous mix-
Catalytic steam reforming occurs over a Ni-based cata- ture comprising CO, H2, CH4, and CO2, with small amounts
lyst at temperatures between 752°C-852°C. It is a two-step of tar and ash. Tar and ash are potential by-products of gasi-
process that includes the shift reaction, and occurs as follows fication and have adverse effects on the process performance
[9]: and downstream end-uses [13]. Char (the unconverted organ-
Bio-oil + H2O → CO +H2 (1) ic fraction and the inert material found in the treated bio-
mass) production arises from the partial oxidation of carbon
and in the feedstock material in the presence of gasifying carriers
CO + H2O → CO2 +H2 (2) (air, oxygen, steam, or CO2), and is largely a mixture of ash
and the unconverted carbon [24]. The main product of gasi-
3.2.2. Gasification fication (producer gas or syngas) is a gaseous mixture of
The gasification process converts carbonaceous materials carbon monoxide (CO), methane (CH4), carbon dioxide
(coal, petroleum coke, biomass, etc.) into combustible gases (CO2), hydrogen (H2), and nitrogen, together with light hy-
(CO, H2, CO2, CH4, etc.) and small amounts of light hydro- drocarbons (ethane, propane) and heavier hydrocarbons (tar),
carbons [37], in the presence of gasifying agents, such as which condense at temperatures within 250°C to 300°C. Im-
oxygen, air, steam, CO2 or their mixtures [25, 36], with impurities such as tar, particulate matter, alkalis, halides, Sul-
purities like nitrogen, sulphur, tars and alkali compounds phur, hydrogen sulfide (H2S), chloridric acid (HCl), and inert
[35]. Bio-oil is produced as an intermediate that gives rise to gases such as nitrogen (N2) are also present. However, the
the final product, syngas. A catalytic or chemical upgrading relative presence of each component, as well as ash and un-
unit is usually coupled to the conversion unit to transform converted carbon depends on the biomass feedstock species,
the gasifying agent, and the operating conditions of the gasi- absence of oxygen and respecting the stoichiometric
fication process [14, 19, 34, 24]. Overall, biomass gasifica- ratio so as to only partially oxidize the fuel.
tion is generally represented as: Biomass + O2 (or H2O)
• Drying (endothermic). Here, the moisture contained
gives rise to CO, CO2, H2, CH4 + other CHs + tar + char +
in the feedstock is evaporated and the heat required
ash + H2S + NH3 + C + trace species [19, 34]. The individual
is proportional to the moisture content of the feed-
chemical reactions that take place during the biomass gasifi-
stock. This process is complete at temperatures
cation process are shown in Table 6 [14, 35].
around 150°C.
Table 6. Typical biomass gasification reactions [14, 35]. • Pyrolysis (endothermic). This process occurs at
temperatures between 250°C to 700°C to produces
lightweight molecules such as solid (char), liquid
Reaction Heating Value (kJ/mol) (tars) and gases (CO, H2, CO2 and light hydrocar-
bons) via the thermochemical breakdown of the bi-
2C + O2 ↔ 2CO +246.4
omass species (the decomposition of cellulose, hem-
C + O2 ↔ CO2 +408.8 icelluloses, and lignin) [34, 35]. Process phenomena
such as heat transfer, series reactions, and product
CH4 + H2O ↔ CO + 3H2 -206
diffusions are involved. The kinetics of the reactions
CH4 + 2H2O ↔ CO2 + 4H2 -165 acts as the rate-limiting step at low temperatures
whereas heat transfer or product diffusion controls
C + CO2 ↔ 2CO -172
the process at high temperatures.
C + H2O ↔ CO + H2O -131
• Reduction (endothermic). Here the products of the
previous stages together with char are reduced
The overall gasification process is grouped into primary, through a series of reactions to produce the final
secondary and tertiary reaction stages based on the tempera- syngas [35]. The reduction temperatures determine
ture ranges and reaction chemistry. Below 500°C, biomass is the final properties or constituents of syngas and the
converted to oxygenated vapor and liquid species, together solid residue.
with water and CO2 during the primary reactions. The sec-
ondary reactions take place between 700°C-850°C to pro- The normal operating temperatures of full-scale biomass
duce CO, H2, CO2, water vapor, phenols, gaseous olefins, gasification vary between 800°C to 1100°C, whereas for
and aromatics, from primary vapor and liquid species. The processes requiring oxygen for the gasification stage, the
produced tar consists of mixed oxygenates, phenolic esters, process temperature ranges from 500°C to 1600°C [24]. The
alkylphenols, heterocyclic esters, and PAHs. Methanation, gasification pathway offers ideal possibilities of combination
steam reforming, cracking, and water gas shift reaction oc- with cheap CO2 capture and storage technologies, giving rise
curs with the remaining gases and tars. At temperatures be- to both primary fuel input flexibility and product mix con-
tween 850°C-1000°C, CO, H2, and CO2 together with water cepts with possibilities achieving zero or even negative car-
vapor, PAHs, and liquid tar results during the tertiary reac- bon emissions [22]. The process enhances the utilization of
tions [19]. biomass and is currently being used to increase the efficiency
and reduce the investment costs of biomass electricity gener-
This process is limited by the biomass feedstock re-
ation through integration with gas turbine technology. A
quirements, homogeneity, bulk density, moisture and ash
combined-cycle gas turbine system is capable of achieving
content, particle size and energy content, which all require
higher efficiencies up to 50%, as the gas turbine’s waste gas-
effective control for efficient gasification [13]. During the
es are recovered to produce steam for the steam turbine [21].
gasification process, the woody biomass is first dehydrated
Apart from its use for heat and power generation, nearly all
before the process temperatures exceed 200°C. Then pyroly-
hydrocarbon compounds, as well as premium fuels (ethanol,
sis is initiated, producing vapor and char. The presence of
methanol, transport fuels, dimethyl ether (DME) and me-
oxygen here oxidizes the char and vapor into a gaseous mix-
thane) and high-value chemicals, can be synthesized from
ture of CO, H2, CO, and water, as well as sulphur, tar, am-
syngas after purification. Syngas can also be upgraded into
monia, and other impurities [13]. The overall gasification
biomethane for injection into the gas grid or converted to
process is endothermic and the biomass oxidation stage nor-
synthetic diesel via the Fischer-Tropsch process, a process
mally provides the required energy through either an auto-
catalyzed by transition metal-based catalysts (Cobalt or iron)
thermal (internal heating of gasifier via partial combustion)
at a higher temperature. Hydrogen can equally be isolated for
or an allo-thermal process (energy supplied from an external
used in fuel cells for electricity generation and to power elec-
source) [6]. The major stages of biomass gasification process
tric vehicles. However, the final end-use of the syngas is
include [6, 24, 25, 35]:
largely dependent on the end demand and plant scale [4, 13].
• Oxidation (exothermic). This is required to generate Also, reacting the clean syngas over a cobalt, platinum or
the thermal energy needed by the endothermic pro- iron catalyst via Fischer-Tropsch pathway gives rise to hy-
cesses (whole process) and to maintain the required drocarbon waxes and long-chain alkanes [37]. The purifica-
operating temperature of the system. It occurs in the tion and upgrading of these products are energy-intensive,
Table 7. Biomass gasification feedstocks [24].
Supply Sector Type Example
Dedicated forestry, forestry by- Short rotation plantations (e.g. willow, popular, eucalyptus), wood blocks, wood chips
Forestry
products from thinning
Herbaceous crops (e.g. miscanthus, reed canary grass, giant reed), oilseeds for methyl
Dry lignocellulosic energy crops, oil,
Agriculture esters (e.g. rapeseed, sunflower), sugar crops for ethanol (e.g. sugar cane, sweet sor-
sugar, and starch energy crops
ghum), starch crops for ethanol (e.g. maize, wheat)
Agricultural residues, livestock Straw, pruning of vineyards and fruit trees, wet and dry manure, industrial waste wood,
Industry
waste, industrial residues sawdust from sawmills, fibrous vegetable waste from paper industries
Dry lignocellulosic contaminated Residues from parks and gardens (e.g. pruning, grass), gemolition wood, organic fraction
Waste
waste of municipal solid waste, biodegradable landfilled waste, landfill gas, sewage sludge
costly and require more R & D to improve their efficiencies value. During this process, the biomass feed loses both its
for large scale use [13]. moisture content and the rigid fibrous structure, resulting in
an increase in the energy density of the material. A combina-
Catalysts play a fundamental role in the gasification
tion of torrefaction and palletization is also possible [19, 24].
products. They improve the gas quality, conversion efficien-
Hydrothermal upgrading (HTU) breakdown biomass using
cy and reduce the tar content. Dolomite, alkaline metal ox-
water as a solvent to produce bio-crude. It is mainly con-
ides, olivine, and Ni-based oxides are widely used gasifica-
ducted in two stages: treating the biomass feed in the water
tion catalysts. Iron, cobalt, ruthenium and potassium-based
at pressures of around 30 bars and temperatures between
catalysts are well known for their role in the Fischer-Tropsch
200°C to 300°C, and the biomass (bio-crude) conversion at
synthesis of diesel, hydrocarbons and other liquid fuels from
temperatures of 300°C-350°C and pressures of 120-180 bar
bio-syngas. However, the performance of these catalysts
and in a variable time period from 5-10 minutes. The pro-
varies and their choice is determined by their properties, re-
action pathways and the desired end product [34]. Dolomite- duced bio-crude is made up of a variety of hydrocarbons that
can be used as a co-fuel in coal plant, for chemicals or syn-
or Ni-based catalysts are used in most gasifiers for the partial
thetic diesel-like fuel production in the chemical industry
tar oxidations, catalytic steam reforming as well as to enable
[24].
the catalytic upgrading of the gasification products into liq-
uid biofuels. This is usually done after effective gas cleaning
and composition adjustments are made [13]. 3.2.2.3. Biomass Gasification Products
The exact constituents of biomass gasification products
3.2.2.2. Gasification Feedstocks and Pretreatments depend on the fuel type and composition, the gasifying me-
The gasifiable biomass feedstocks (Table 7) are com- dium or gasifier design, the temperature, operating pressure,
posed of cellulose, hemicellulose, lignin, and proteins, with fuel moisture content and the way the reactants (biomass fuel
their percentage composition in softwood, hardwood, and and gasifying agent) are brought into contact within the gasi-
straw indicated in [24]. The fibers of biomass (cellulose and fier. As such, it is impossible to predict the exact composi-
hemicellulose) consist of saccharides that polymerize into tion of biomass producer gas [34]. Straw produces a high
long chains. Lignins are phenolic polymers which play a hydrogen content, highest char content in softwood biomass,
pivotal role in ensuring the structural stiffness of proteins lowest char content in straw, higher dust content in straw and
and also functions as the fibers glue. Mainly the herbaceous higher tar content in hardwood [24]. The feedstock proper-
species produce proteins [24]. These feedstocks are broadly ties with a strong influence on the gasification process are
classified as wood and residues, agricultural and herbaceous, moisture content, ash content, volatile matter, char, organic
marine biomass, human and animal waste, contaminated and constituents, thermal conductivity, and inorganic constituents
industrial biomass waste, and biomass mixtures [19]. [6]. The gasification product can be in a solid phase, and a
gas/vapor phase - often split into a gas and a condensable
Biomass pretreatment is aimed to provide homogeneous
phase. The solid phase (ash) is made up of the unreacted char
feedstocks with respect to composition, size and moisture
and the inert materials found in the feedstock, with char hav-
content (25-30wt.%) required for the smooth and efficient
ing ˂1wt.% in the quantity of ash. Char has a carbon content
operation of the gasification process. Apart from drying, the
greater than 76%, making it possible for its direct industrial
other gasification pretreatment methods are torrefaction and
use. In the gas/vapor phase (syngas), the gas phase comprises
hydrothermal upgrading (HTU) [24]. Torrefaction occurs in
of an incondensable gaseous mixture of CO, H2, CO2, CH4,
the absence of oxygen at temperatures between 200°C to
light hydrocarbons, and some C2-C4 hydrocarbons, at room
300°C, under an inert atmosphere to enhance biomass poten-
temperature as well as minor quantities of NH3, H2S, and
tials for gasification through moisture, hydrogen and oxy-
HCl depending on the feedstock composition. They can be
genated species loss. As a form of mild pyrolysis, it poten-
burnt for electricity or heat generation, or use to synthesize
tially enhances biomass resistance to moisture and its heating
Table 8. Classes of tar [24].
Tar Type Type Name Peculiarity Characteristic Compounds
-Determined by subtracting the GC-detectable tar

1 GC-undetected Very heavy tars, cannot be detected by GC
fraction from total gravimetric tar
Tars containing heteroatoms, highly water-soluble -Pyridine, phenol, cresols, quinoline, isoquinoline,
2 Heterocyclic aromatics
compounds dibenzo phenol
Usually light hydrocarbons with a single ring; do not

3 Light aromatics (1 ring) -Toluene, ethylbenzene, xylenes, styrene
pose a problem regarding condensability and solubility
Light PAH compounds 2 and 3 ring compounds; condense at low temperature -Indene, naphthalene, methylnaphthalene, biphenyl,
4
(2-3 rings) even at very low concentration acenapthalene, fluorene, phenanthrene, anthracene
Heavy PAH compounds Larger than 3 rings, these compounds condense at high -Fluoranthene, pyrene, chrysene, perylene, coro-
5
(4-7 rings) temperature at low concentration nene
liquid transport fuels, hydrogen or chemicals. The quantity arise from the recombination and decomposition of primary
of syngas produced on dry mass basis may range from 1-3 tars in the syngas reducing environment. They also do not
Nm3/kg, with a low heating value (LHV) range between 4-15 co-exist with primary tars, but only appears when all the
MJ/Nm3. primary tars are converted into the secondary tars [24]. Fig.
(3) depicts a schematic representation of the different classes
In the production of gaseous fuels from biomass, char
of tars as a function of temperature.
gasification determines the rate of the process (rate-limiting
step) [24, 34]. The condensable phase (tar), consist of vari- 3.2.2.4. Syngas Processing
ous organic compound which is considered as bituminous oil
in condensed form. Tar (a complex mixture of condensable Synthetic gas, a raw material for biofuels, chemicals and
hydrocarbons), according to the European board of standard- power generation, usually contains impurities such as tar,
ization refers to all organic compounds present in syngas particulate matter, nitrogen (NH3, HCN), alkali, halides, sul-
with defined analysis procedures, except the gaseous hydro- phur (H2S, COS) and trace elements mainly responsible for
carbons C1-C6. The composition of tar is strictly dependent gasifier clogging, corrosion and catalyst deactivation. Thus,
on the gasification technology used, the operating conditions rendering syngas unfit for Fischer-Tropsch synthesis, bio-
and the biomass feedstock. They are generally divided into methanol production, fuel cell uses, and other applications.
five major groups (Table 8) according to their molecular The majority of syngas is used for ammonia synthesis (50%),
weights [24]. In the gasification process, tar originates from bio-hydrogen production (25%), and the remaining used for
the pyrolysis stage and are subject to decomposition and bio-methanol production, FT synthesis, and other processes.
recombination. They are classified as primary, secondary and The processes for syngas cleaning are broadly classified as
tertiary tars according to their respective formation mecha- cold or hot gas clean-up based on the condensation tempera-
nisms. The primary tars are dependent on the biomass feed tures of its various constituents. Some of these impurities
and are produced directly during the pyrolysis step. Primary and their cleaning processes are discussed in [19].
tars containing oxygenated compounds (carbon acids, alde- Biomass gasification for power generation produces
hydes, alcohols, ketones, etc.) arise from cellulose and hemi- mainly flue gases and unwanted by-products such as ashes
cellulose feedstocks due to their high oxygen contents. Lig- and tar (gasification bottleneck) which are often left unu-
nin pyrolysis principally gives rise to aromatic compounds, tilized especially tar despite its rich fuel and chemical poten-
mainly bi- and tri-functional substituted phenols (xylenol, tials. Due to the complex nature of gasification tar with hun-
cresol, etc.) [24]. dreds of chemical constituents, there has been a recent inter-
The secondary tars are produced during the oxidation est in the valorization of this biomass gasification waste to
stage. They are alkylated mono- and di-aromatics, as well as liquid fuels and chemicals, given its high potential for soil
hetero-aromatics such as furan, pyridine, thiophene, and di- contamination when discharged to the environment untreated
oxin. Their formation arises from the transformations of pri- [23]. However, the complete treatment, removal or conver-
mary tars through rearrangement reactions (dehydration, sion of tar is a huge technical challenge (low efficiency, foul-
decarbonylation, and decarboxylation), at temperatures ing, plug pipes and tubes, operational difficulty, etc.) in the
above 500°C and in the presence of an oxidant such as air, development and in the successful application of biomass-
oxygen or steam [24]. At temperatures above 800°C, tertiary derived gas. Some commonly used methods are: end pipe tar
tars (also known as recombination or high-temperature tars) syngas clean-up, in bed catalytic tar reforming and in bed
are formed. They comprise mainly of aromatics and polynu- thermal tar cracking processes [24]. Catalysts play a key role
clear aromatic hydrocarbons (PAH) such as naphthalene, in enhancing reaction rates at low temperatures and also
benzene, pyrene, benzopyrene, and phenanthrene. Biomass promote the conversion of tar into valuable combustible gas-
gasification generally does not produce tertiary tars but they es through steam reforming, thermal cracking, dry reform-
Fig. (3). Representation of tar classes as a function of temperature [24]. (A higher resolution / colour version of this figure is available in the
electronic copy of the article).
ing, hydrocracking, water-gas shift reactions, and hydrore- Four main processes (carbonization, aqueous phase re-
forming. They are used either as bed materials or as feed- forming (APR), liquefaction and gasification) make up hy-
stock additives [25]. drothermal processing (Table 9), with water acting as a reac-
tant, solvent, and a catalyst [5, 13]. Hydrothermal carboniza-
At present, biomass gasification is mainly focusing on
tion (HTC) is the mildest, occurs at pressures between 20 bar
the production of low- or medium heating value fuel gas for
to 40 bar and temperatures between 180°C to 250°C to pro-
use in the internal combustion engines for power generation.
duce hydro-char (solid), which is similar in properties to
Lesser research has so far been documented on gasification
for liquid transport fuels or chemicals generation. Gasifica- low-rank coal. This process is governed by temperature and
tion is a very promising technology for biomass valorization residence time and allows for the reduction of both the oxy-
gen and hydrogen content of the biomass feedstock via de-
with high flexibility and efficiency. The promotion of this
hydration and decarboxylation reactions [39]. Hydrothermal
technology in the future requires advanced, cost-effective,
liquefaction (HTL) occurs at pressures up to 180 bar and
and highly efficient gasification systems and processes. This,
temperatures between 250°C and 375°C to produce liquid
therefore, ushers need for further research and development
bio-crude, which can be upgraded via catalytic hydro-
in biomass gasification in order to improve the future per-
treatment to a wide range of distillate petroleum-derived
formance of this technology necessary to enhance the pro-
products. Hydrothermal gasification (HTG) or supercritical
cess efficiencies, improves gas quality and purity, and to
water gasification (SCWG) occurs at pressures beyond 200
lower the investment costs. To achieve these, the develop-
bar and temperatures above 375°C in the absence of oxidants
ment of innovative catalysts, sorbent, and high-temperature
filtration media are fundamental requirements, coupled with to produce syngas, CO2, CH4 and C1-C4 hydrocarbon gases
high-temperature gas cleaning and catalytic conditioning. like C2H4 and C3H6 [13, 30]. At low temperatures, by-
products like small bio-oil, tar and char are formed. The
aqueous phase reforming (a subsection of HTG) takes place
3.2.3. Hydrothermal Processing of Biomass
within a temperature range of 220°C-250°C and pressures
Biomass hydrothermal conversion has drawn much atten- 1.5-5 MPa to generate H2 syngas, alkanes and a range of bio-
tion since the adoption of hydrothermal energy as a high based chemical products including fibers and plastic chemi-
potential energy resource. At first, much focus was on the cals [5].
selection of the right solvent and mainly on high temperature
These processes produce a broad range of chemicals and
and pressure processing materials, given the omission on
fuels in the gaseous, liquid or solid state with opportunities
compound solubility knowledge and its effect on the overall
for carbon capture, storage, and sequestration, have high
process [5]. It is an excellent approach for converting high
conversion rates, and most importantly uses wet biomass
moisture energy-rich biomass into various products, such as
without any prior dewatering [5]. Despite these benefits of
solid (biochar), a liquid (bio-oil), or a gas (hydrogen, me-
hydrothermal biomass processing, it uses more complex and
thane, etc.) [30]. This involves the heating of organic wastes
expensive reactors, requires large water handling equipment
or aqueous biomass slurries at higher pressures and low or
and capabilities, challenging to manage large-scale separa-
moderate temperatures to generate a high-density energy
tion and extraction processes and also difficult to compute
carrier or liquid product in the presence of a catalyst [21],
gas yield due to a complex mass balance resulting from the
using the subcritical and supercritical water as the processing
variabilities in the hydrothermal media [28, 30]. The hydro-
media [5]. The basic processing conditions are high pres-
thermal biomass processing takes place under two main pro-
sures (4-22 MPa) and temperature between 250-374°C. This
cess conditions: the subcritical and supercritical water condi-
process low temperatures, low tar yield, and high energy
tions, which are each determined by the critical point of wa-
efficiency compared to other thermochemical processes are
ter (374°C and 22.1 MPa). Table 10 shows the various prop-
the key factors responsible for the recent widespread interest
erties of water at these process conditions. Biomass constitu-
in this technology [28], [38]. Suitable feedstocks are those
ents like cellulose and lignin are insoluble in water at ambi-
with high ash and moisture contents such as manures, food
ent temperature but are soluble in supercritical water (high-
wastes, anaerobic digestion digestate, sewage sludge, aquatic
temperature water). The hydrothermal breakdown of biomass
biomass (micro- and macroalgae) and municipal wastes. The
takes place as follows: the water-soluble biomass portion
slurries can be fed up to 30wt.% solids [13].
disperses into the water at about 100°C, and above 150°C
Table 9. Main hydrothermal processes and operating conditions [5].
Hydrothermal Pressure Reaction

Temperature (K) Catalyst Main Product
Reaction (MPa) Time
HT carbonization
Low temperature 523 2 Several hours Not essential Hydrochar
High temperature 573-1073 2 Several hours Optional hydrochar
HT liquefaction
High temperature 553-643 10-25 Few seconds Optional Bio-oil
Alkaline salts: Na2CO3, KCl, KOH, Increasing bio-oil yield,

Low temperature 573-873 10-25 Few seconds heterogeneous catalysts under high improved to transport fuel
pressure H2 by increasing C/H ratio
HT gasification
Near-critical 573-773 Various Few seconds Metal catalysts and alkaline salts CH4
Syngas H2 with minor,

Supercritical 773-1073 Various Few seconds Metal catalysts and alkaline salts
CO2, C1-C4 gases
Aqueous phase re- Pt/Al2O3, Pt/ZrO2, Rh, Ni and on SiO2, H2 and CO2 with minor
493-523 1.5-5 Few seconds
forming etc. C1-C6 alkanes
Table 10. Properties of water under ambient, subcritical and supercritical conditions [28].
- Ambient Water Subcritical Water Supercritical Water
Temperature, T (°C) 25 250 400 400
Pressure, p (MPa) 0.1 5 50 50

-3
Density, ρ (g cm ) 0.997 0.80 0.17 0.58
Dielectric constant, (ε) 78.5 27.1 5.9 10.5
pKsu 14.0 11.2 19.4 11.9

-1 -1
Heat capacity, cp (kJkg K ) 4.22 4.86 13 6.8
Viscosity, µ (mPa s) 0.89 0.11 0.03 0.07
Thermal conductivity λ (mWm-1K-1) 608 620 160 438
hydrolysis occurs. The solid biomass is transformed into the 3.2.3.1. Hydrothermal Liquefaction (HTL)
slurry at about 200°C and 1 MPa, and finally, at about 300°C
and 10 MPa, liquefaction takes place giving rise to the oily This is one of the most investigated hydrothermal pro-
products. Here, biomass is converted into a solid (biochar, a cesses for the conversion of waste biomass into chemicals
liquid (bio-oil) and gaseous products via the variation of the and bio-based fuels at moderate temperature and high pres-
process conditions like temperature, reactor pressure, reac- sure enough to keep the water in the liquid phase [5]. Hydro-
tion time and catalyst presence [28]. Supercritical water oxi- thermal liquefaction is a promising technology for the pro-
dation is used for the removal of toxic compounds (pollu- duction of high-quality bio-oil from biomass. Here, mainly
tants) from biological and organic waste, and in power gen- wet feedstocks or those with high moisture content are used.
eration cycles for power generation. To better understand This eliminates the need for feedstock drying (energy-
biomass hydrothermal processing and the various degrada- consuming) as performed with traditional thermochemical
tion pathways, a thorough knowledge of water properties processes such as gasification and pyrolysis, that requires
under hydrothermal conditions (subcritical and supercritical) only dry feedstocks [7]. This process is performed in water
is required. At higher temperatures, water has a low dielec- under moderate temperature of about 280-370°C and at high
tric constant. As such, under supercritical conditions, water pressures (10-25 MPa), to generate liquid bio-crude with
is a very good solvent for non-polar substances but these high energy content, together with aqueous, gaseous and
substances are insoluble in water at room temperatures [28]. solid-phase by-products [30, 38]. This involves several com-
plex reactions, giving rise to high energy density products rise to by-products such as CO2 and nutrients which are re-
and an enhanced heat recovery process. Two major feedstock used for algal cultivation in the algal culture for growth and
classes characterized the process mechanism. These are the photosynthesis, and wastewater which can be reused to re-
dry feedstocks (lignocellulose biomass) comprising of cellu- duce the process water need, as well as organic fertilizer for
lose, hemicellulose and lignin constituents, and the wet feed- agricultural use. The process generates about 85-90% of en-
stocks (algal biomass) made up of vital components such as ergy, consuming only 10-15% of the feedstock energy, thus a
proteins, carbohydrates, lipids and algaenans [38]. A broad very energy efficient process. Moreso, the resultant bio-
range of chemicals can be obtained through HTL alongside crude is very similar to their petroleum counterparts, and
bio-crude. These mainly consist of monoaromatic com- thus require very little upgrading for commercial use [38].
pounds, fatty acids, alkenes, alkanes, polyaromatic com- All the above-listed by-products and applications if properly
pounds, nitrogenous and other oxygenated compounds, de- valorized, can potentially overcome the economic challenges
tailly constituted by [38]. In this section, key concepts of of HTL. However, further research to optimize the process
HTL such are the process principles, bio-crude elemental mechanisms and parameters are still needed to overcome the
composition, feedstock types, process energy efficiency, as setbacks of HTL and to effectively commercialize the pro-
well as, future scope and prospects, are highlighted. cess.
HTL gives rise to four distinct product phases comprising During the process, water is kept in the liquid phase by
of the bio-oil, light gases, CO2 and trace amounts of CH4, operating at or above its saturation point which greatly min-
CO and H2, a solid residue, char, and a carbon-rich water imizes the enthalpy change linked with the latent heat of
phase [7]. As discussed in a study [40], process parameters, vaporization of water [13]. In the past decades, compressed
such as temperature, pressure, feedstock composition, resi- hot water has attracted much attention as a green reaction
dence times, heating rate, water ratio, catalyst, particle size, medium. Presently, it is widely applicable in resource recov-
solvent density and type, and reaction medium, greatly affect ery from wastes, polymers recycling, and biomass energy
bio-oil yield. The bio-oil generated can be improved into recovery, waste treatments, homogeneous and heterogeneous
high-quality liquid fuels via chemical, catalytic and physical catalysis, inorganic and organic materials synthesis, and oth-
(extraction, solvent addition, or separation) methods. This ers [5]. When the process occurs below the critical point of
process is advantageous in that it uses wet biomass which water, it is known as subcritical. The supercritical process
does not require drying, uses water which is a unique and takes place above water critical point (274°C and 22.1 MPa),
environmentally friendly solvent, occurs at lower tempera- with the water properties within the liquid-like and gas-like
tures, highly energy-efficient and does not require drying phase. Under these conditions, water functions both as a sol-
[28, 31], produces high quality bio-oil, higher yields, lower vent and a catalyst or reactant. Its dielectric constant de-
water and oxygen content, which give it an HHV compared creases, raising the solubility of insoluble organic com-
to pyrolysis or gasification oil but higher compared to fossil pounds. Also, the reaction rates are higher due to the high
fuels. However, the high-pressure process leads to high diffusion coefficient as the water viscosity decreased [7].
equipment cost for large-scale or industrial processing [7].
In the past few decades, there has been a strong drive and
The low oxygen content and HHV of the bio-oil main prod-
interest in the use of biomass and biomass derivatives for the
uct originates from the high contribution of the dehydration
production of liquid fuels. Research studies within this scope
and decarboxylation reactions in the HTL process, removing
range from biomass gasification, pyrolysis, HTL of lignocel-
oxygen in the form of water and CO2 respectively [40],
lulose material and the upgrading processes of the derived
which reduces biomass oxygen from 40wt.% to about
bio-crude. The choice of biomass generates high prospects
10wt.% [5]. According to [7], increasing the HTL process
and expectations for fuels, fine chemicals and raw material
temperature correspondingly raises bio-oil yield prior to the synthesis for the petrochemical industry. Among the biomass
occurrence of bio-oil cracking and repolymerization reac-
to fuels and chemicals processing methods, the HTL has
tions that lead to an opposite trend. In addition, increasing
drawn huge attention recently as one of the promising routes
the residence time (normal range of 5-30 minutes) equally
for both dry and wet biomass [38]. Presently, fuels (biofuels)
increases bio-oil yield. However, a further increase in the
and chemicals production rely mainly on dry biomass feed-
reaction time rather leads to a decrease in bio-oil yield origi-
stocks (dry wood) through various pyrolysis and gasification
nating from cracking and repolymerization reactions to form
processes. Only very little interest and attempts are reported
lighter gases and char respectively. A detailed review of the
[38] which have so far been made towards the development
techniques for the separation and extraction of HTL prod-
of the HTL process for wet biomass valorization, despite the
ucts, chemical composition and products analysis using the
huge prospects in wet biomass feedstocks. Microalgae due to
mass spectroscopy, Fourier transform infrared (FTIR) spec-
their high photosynthetic efficiency, fast growth rate, maxi-
troscopy, elemental analyzer, nuclear magnetic resonance mum biomass production, and the lack of arable land re-
(NMR) spectroscopy, high performance liquid chromatog- quirements, is regarded as an excellent fuel and chemical
raphy (HPLC), etc. are discussed in [28].
source through wet biomass processing. Thus, the selection
The HTL process mainly converts biomass to bio-oil of the best process feedstocks and operational conditions, as
which can substitute fossil fuels. This process is however well as the optimization of the existing parameters and pro-
challenged by its high-pressure conditions, making its eco- cess mechanisms to enhance HTL process efficiency and
nomics very questionable. The HTL of algal biomass gives yields are very important for enhancing future performance,
Fig. (4). Pathways for the HTL of lignocellulose biomass [38]. (A higher resolution / colour version of this figure is available in the electron-
ic copy of the article).
Fig. (5). Pathways for the HTL of wet biomass [38]. (A higher resolution / colour version of this figure is available in the electronic copy of
the article).
prospects and applicability of this technology especially for tential for nutrient recycling. Fig. (5) depicts a schematic
wet biomass, as well as in assuring the economic viability of representation of wet biomass hydrothermal processing.
HTL. Here, the algae biomass feed from an algal culture is first
dewatered to obtain a feed slurry with about 20% solid,
3.2.3.1.1. Dry biomass HTL which is then pumped into the HTL unit to produce bio-
This produces bio-crude either in a continuous or batch crude which is then further hydrotreated to generate fine
reactor, with detailed pathways as shown in Fig. (4). The hydrocarbon fuels. The CO2 and nutrients that result from
feedstock is pretreated to reduce the particle size, removes the aqueous phase are re-used for algal cultivation, making
impurities and to make a stable slurry for easy pumping the process more economically viable and sustainable [38].
through alkaline treatment. The HTL process then takes
3.2.3.1.3. HTL Process Mechanism
place at around 350°C and 150 bar for around 15 minutes,
followed by phase separation to produce a gaseous mixture Prior to the degradation of the biomass constituents into
of CO2, bio-crude, solid residue and traces of the aqueous smaller molecules via dehydrogenation, dehydration, decar-
phase (water) which can be re-used in the HTL unit to en- boxylation, and deoxygenation, the biomass feedstock is
hance the yield of the bio-oil or reduce the process water initially fragmented by hydrolysis. Repolymerization of the
requirement. Anaerobic or catalytic hydrothermal gasifica- lighter molecules results in the synthesis of some complex
tion treatment of the other water stream results in a hydro- chemicals, containing aldehydes, phenols, acids, ketones,
gen-rich or methane-rich syngas. However, the presence of alcohols, esters, and other aromatics [38]. HTL is initiated by
phenols and furfurals limits the anaerobic treatment process. solvolysis of biomass in micellar forms, followed by the dis-
The resulting bio-crude has less moisture and oxygen con- integration of biomass major polymeric constituents (cellu-
tent, thus can be used directly or upgraded by further hydro- lose, hemicellulose, and lignin), and then concludes with its
treatment for commercial use. This process is highly energy- thermal depolymerization into smaller fractions [30]. The
efficient as the overall heat generated can be used efficiently actual mechanism of HTL is still unclear. However, the pro-
and effectively to operate the hydrothermal gasifier [38]. cess comprises depolymerization, preceded by decomposi-
tion and recombination reaction. The biomass is first decom-
3.2.3.1.2. Wet biomass HTL posed and depolymerized into highly reactive lighter mole-
The HTL of wet/algae biomass differs only slightly (no cules (water-soluble oligomers), preceded by the cleavage of
pretreatment) from that of dry biomass and offers great po- the inter- and intramolecular hydrogen bonds to produce
simpler monomers (glucose and other products like acetic reactions via cyclization, polymerization, and condensation
acid, furfural, and aldehyde compounds) [30], which subse- gives rise to the final products. This group of catalysts pref-
quently repolymerizes to form bio-crude, gas, and solids. erentially decreased solid yields, increased bio-crude yield
Due to the complex nature of biomass, the process mecha- and properties and decreased dehydration reactions (with
nism and reaction chemistry is also complex and the major elevated pH) that produces unstable and unsaturated mole-
process parameters like residence time, temperature, process cules. However, the recovery of these catalysts is costly,
decomposition, condensation and repolymerization of the owing to the energy and cost-intensive separation process
constituents also vary within the phases [38]. Temperature, [30]. Heterogeneous catalysts are most commonly used in
pressure, particle size and resection times affect bio-oil pro- HTG, with only a few applications so far with HTL especial-
duction via HTL [30]. ly with the improvement of the bio-crude quality from ligno-
cellulose biomass. Platinum, nickel, and palladium are com-
Biomass depolymerization sequentially dissolves the
mon heterogeneous catalysts, but due to the rareness of these
polymeric components of biomass, aided by their physico-
metals, attention has been shifted to metallic oxides like
chemical properties. The process temperature and pressure
ZrO2, MnO, MgO, NiO, ZnO, CeO2, La2O3, and so on [30].
modify the polymer long-chain structure, while the organic
materials’ energy contents are recycled in the presence of The very first catalytic hydrothermal liquefaction of
water [38]. wood biomass with CsOH and RbOH (very potent bases) has
been performed [41] and noted that these strong bases
The decomposition of the biomass monomers occurs via
dehydration, cleavage, deamination, and decarboxylation. (CsOH and RbOH) like other base catalysts greatly improve
Here, water molecules are lost via dehydration, CO2 lost by oil yields by hindering char formation, producing mainly
benzenediol derivatives and phenolic compounds. Also, Ka-
decarboxylation and deamination removes the amino acid
ragöz et al., [42] investigated the effect K and Na carbonates
content. The decarboxylation and dehydration processes re-
and hydroxides on the product yields and boiling point dis-
move oxygen from biomass as CO2 and H2O respectively,
tribution of oxygenated hydrocarbons from low-temperature
and this hydrolysis converts the polymers to polar monomers
HTL of wood biomass (pine). They found that the treatment
and oligomers. The applications of water at high temperature
of wood biomass with catalytic alkaline solutions (NaOH,
and pressure dissociates the hydrogen-bonded cellulose struc-
Na2CO3, KOH, and K2CO3) produces mainly phenolic com-
ture into its glucose monomers. The isomerization, hydroly-
pounds whose distribution depends solely on the exact base
sis, reverse-aldol breakdown, dehydration, recombination
solution used and thermal treatments produce mainly furan
and rearrangement reactions of fructose compared to glucose
results in a broad stream of products like furfural, polar or- derivatives. They reported the catalytic activity of these ba-
ganic molecules, phenols, organic acids, and glycoaldehydes, ses as follows: K2CO3>KOH>Na2CO3>NaOH. The effects of
various catalysts and process parameters on the product
which are highly water-soluble [28, 38]. Among these reac-
yields, distribution and chemical constitution from various
tions, the decomposition and deoxygenation reactions are the
biomass streams like bagasse [43], waste biomass [44], food
key reactions that give rise to the resulting biocrude, consist-
waste using CeZrOx [45], aquatic biomass [46, 47], and bar-
ing of acids, aldehydes, and aromatics [40].
ley straw [48] are also reported in literature. The use of bi-
The repolymerization and recombination stage arises functional catalysts like Ni/HZSM-5 [49] has also been in-
from the non-availability of hydrogen compounds in the sys- vestigated and seen to exhibit better catalytic activity on bio-
tem. As such, with high concentrations of free radicals (reac- oil production as it integrates the cracking and hydrodeoxy-
tive fragments from previous reactions), the fragments tend genation reactions. The production of feedstocks for other
to repolymerize or recombine into heavier char molecules, biomass conversion technologies like gasification is also
noted for their coke formation. However, with sufficient feasible with catalytic HTL. This has been demonstrated [50]
presence of hydrogen in the organic mixture during the liq- by using K2CO3 catalyst to produce aqueous gasification
uefaction process, stable weight species will be formed from liquids and gases from pine sawdust. This in a nutshell inte-
the capping of the free radicals with the hydrogen molecules grates a biomass to liquid gasifier to a catalytic HTL process
[38]. and this improves the overall gasification efficiency. Bi-
ocrude quality in algae HTL is best improved using Ni/SiO2-
3.2.3.1.4. Catalytic Hydrothermal Liquefaction
Al2O3, Ni-Mo/Al2O3, Pt/C, Pt/Al2O3 and Ce/HZSM-5 cata-
Homogeneous and heterogeneous catalysts are generally lysts, with Ce/HZSM-5 catalyst presently seen as the first-
employed in HTL to enhance the process efficiency through choice option. The highest catalytic denitrogenation, deoxy-
the reduction in tar and char formation while improving oil genation and desulfurization activities are exhibited respec-
(product) yields. The homogeneous catalysts (alkali salts, tively by Ce/HZSM-5, Co/Mo/Al2O3 and Ni/SiO2-Al2O3.
with the K salts more active than Na salts) like KHCO3, Also, Ru supported catalysts like Ru/C, Ru/C+alumina, show
KOH, K2CO3, Na2CO3, and NaOH, improve the product higher deoxygenation, denitrogenation, and hydrogenation
yield of the HTL process by facilitating water-gas shift reac- performances in biocrude upgrading whereas Pt supported
tions through ester formation via decarboxylation reaction catalysts, such as Pt/C and Pt/γ-Al2O3 showing optimal cata-
between biomass hydroxyl groups and the formate ions in lytic activities in heteroatom content reduction and in im-
the alkali carbonates, followed by dehydration, deoxygena- proving algal HTL biocrude quality and upgrading, especial-
tion, decarboxylation and dehydration of micellar-like frag- ly with respect to catalytic hydrogenation, deoxygenation
ments into lighter ones. Then, the cycle of rearrangement and denitrogenation [47].
4. CURRENT DEVELOPMENTS AND FUTURE OF benefits and sustainability. Efficient feedstock upgrading and
BIOMASS CONVERSION PROCESS refining processes would be employed in future biorefiner-
4.1. Current Developments ies. This would greatly improve biorefinery efficiency given
the added uniformity of the process with the fractionating of
Current research and development in renewable energy the biomass feedstock into its core constituents before usage.
technologies have led to significant engineering advances As such, a complete biomass usage will be assured as only
and discoveries for all renewable energy resources. Some of the residual biomass shall be used for heat and power gen-
these advances in biomass conversion technologies are [22]: eration. Nanoparticles-based catalysts would more likely be
• Advanced biorefinery system designs for the sus- used to improve the catalytic upgrading/cracking processes
tainable production of multiple products. of the products of biomass thermochemical conversion. Also,
greener processes with higher efficiencies shall be applicable
• Advanced gasification processes for the efficient for biomass conversions under mild conditions through bio-
production of medium energy content fuel gas and catalysts development.
power.
Biodiesel and bioethanol in the near future completely
• Advanced plantation designs for multicultivation of replace gasoline, given the unlimited scope and rapid ad-
virgin biomass species for integrated biomass pro- vances of biomass biochemical processing and algal biomass
duction and conversion systems. conversion processes. In addition, the production efficiencies
of cellulases and hemicellulases shall be improved through
• Closed-coupled biomass gasification-combustion genetic engineering (genetic manipulation) and this would
systems for the production of steam and hot water greatly reduce the conversion times for the biochemical pro-
for schools and commercial buildings. cessing of lignocellulosic biomass. Furthermore, transgenic
• Advanced catalysts for thermochemical gasification plants with less lignin content and an upregulated biosynthe-
for high yield chemicals, gases, and fuels production. sis of cellulose shall be grown. These plants would have the
capacity to capture and store more carbon so as to enhance
• Zero-emission biomass waste combustion systems the energy density of biomass. Conclusively, the bright fu-
for energy recovery, waste disposal, and recycling. ture of biomass to energy conversions is evident with the
vast number of integrated biorefineries already planted glob-
• Fast pyrolysis processes for liquid fuels and chemi-
ally [3].
cals production from biomass
• Genetically engineered microorganisms for the sim- CONCLUSION
ultaneous conversion of pentose and hexose sugars
Biomass can be converted to solid, liquid, and gaseous
to ethanol for cellulosic biomass
fuels and high-value chemicals or high-density energy and
4.2. Future of Biomass Processing chemical precursors. Biomass energy is released directly
through combustion or co-firing with fossils (natural gas or
Biomass has the full potential to provide a cost-effective coal) for heat and power generation, or indirectly through
and sustainable supply of energy in the future, while simul- thermochemical processes (gasification, pyrolysis, liquefac-
taneously helping countries to meet their targeted GHG tion, etc.) to produce fuels (syngas, bio-oils, charcoal, etc.)
emission reduction. Biomass integrated gasification-gas tur- and value-added chemicals or intermediates. The vast array
bine technology with high energy conversion efficiencies of biomass feedstocks for chemicals and biofuels production
holds the future of biomass electricity generation. The re- vary substantially with respect to their physicochemical con-
newable, flexible and adaptable biomass resource is expected stituents, which greatly influence their choice of conversion
to favorably compete for niches with fossils in the chemical technology.
industry. However, the success of the biomass-derived chem-
A number of processes transform biomass into fuels and
icals depends on the demand and supply of feedstock, prima-
chemicals. However, all these processes show some major
ry chemicals and key intermediates such as lactic acid, cellu-
shortcomings. This ushers the need for a modern biorefinery
lose, levulinic acid, etc, that the petrochemical industries
to maximize environmental and economic benefits through
shall be unable to make [21]. Biomass resource, with its
the combination of the various processes. The use of small,
great natural abundance, is a perfect substitute for fossil fuels
local or mobile pyrolyzers could make the transformation of
for energy generation if fully harnessed. Third and fourth
agricultural waste and forestry materials into liquid attractive
generation biofuels processing technologies shall have great
and this can easily be shipped and further processed in a cen-
future prospects and impact on climate change mitigations,
tral biorefinery. Biomass conversion technologies comprise
thereby creating a more carbon-neutral environment free
of both biochemical and thermochemical processes, suitable
from greenhouse gases.
for both direct conversion or the formation of high energy or
The present biorefineries generate and attempt to gener- chemical intermediates. The sufficient variability of these
ate costlier fuels and value-added products (chemicals) with processes enabled the gaseous or liquid fuels produced to be
an almost negligible cost of the initial raw materials, making identical or non-identical to fossil fuels. Virtually, all fossil-
biomass processing a great attraction to investors in the derived fuels and chemicals can be produced from biomass.
chemical and energy industries owing to its potentially huge The modern biorefinery uses almost all of the processes in-
volved in the refining of petrochemicals and fuels in the pe- [http://dx.doi.org/10.1016/j.rser.2014.07.129]

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Biomass Conversion to Fuels and Value-Added Chemicals: A Comprehensive

Article · October 2019

Erasmus Muh Fouzi Tabet

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Biomass Conversion to Fuels and Value-added Chemicals: A Comprehen-

Erasmus Muh1,*, Fouzi Tabet2 and Sofiane Amara3

1. INTRODUCTION resource, relatively cleanest and most abundant among the

2405-4631/20 $65.00+.00 © 2020 Bentham Science Publishers

Component Percent Dry Weight (%) Description

Table 2. Classification of biofuels [3, 19].

Biofuel type Description Examples

• Biogas from waste and residues

Produced from aquatic micro- • Algal biodiesel

Biofuels based on high solar efficiency • Carbon-negative technology

Fast ̴ 500°C. Shot hot vapor residence time ˂2s 75 12 13

Intermediate ̴ 500°C. Moderate hot vapour residence time 5-30s 50 (2 phases) 25 25

Gasification (allothermal) ̴ 750-900°C. Moderate hot vapour time >5s 3 1 96

0, unless vapours are con-

Table 4. Chemical constituents of fast pyrolysis liquid [9].

Major Components Mass %

Lignin fragments: insoluble pyrolytic lignin 15-30

Aldehydes: formaldehyde, acetaldehyde, hydroxyacetaldehyde, glyoxal, methylglyoxal 10-20

Carbohydrates: cellobiosan, α-β-levoglucosan, oligosaccharides, 1,6-anhydroglucofuranose 5-10

Phenols: phenol, cresols, guaiacols, syringols 2-5

Alcohols: methanol, ethanol 2-5

Ketones: acetol (1-hydroxy-2-propanone), cyclopentanone 1-5

Physical Properties Pyrolysis Oil Diesel Fuel

Moisture content 20-30wt% 0.1wt%

Density 1.2kgL-1 0.94kgL-1

Elemental analysis (wt%)

Ash 0-0.2 0.1

HHV as produced 16-19 MJkg-1 40 MJkg-1

Viscosity 40-100 cp 180 cp

Solids (char) (wt%) 0.1-0.5 1.0

Vacuum distillation residue Up to 50 wt% 1 wt%

Table 7. Biomass gasification feedstocks [24].

Supply Sector Type Example

Table 8. Classes of tar [24].

Tar Type Type Name Peculiarity Characteristic Compounds

-Determined by subtracting the GC-detectable tar

Usually light hydrocarbons with a single ring; do not

Table 9. Main hydrothermal processes and operating conditions [5].

Hydrothermal Pressure Reaction

Low temperature 523 2 Several hours Not essential Hydrochar

High temperature 573-1073 2 Several hours Optional hydrochar

High temperature 553-643 10-25 Few seconds Optional Bio-oil

Alkaline salts: Na2CO3, KCl, KOH, Increasing bio-oil yield,

Syngas H2 with minor,

- Ambient Water Subcritical Water Supercritical Water

Temperature, T (°C) 25 250 400 400

Pressure, p (MPa) 0.1 5 50 50

Dielectric constant, (ε) 78.5 27.1 5.9 10.5

pKsu 14.0 11.2 19.4 11.9

Viscosity, µ (mPa s) 0.89 0.11 0.03 0.07

Thermal conductivity λ (mWm-1K-1) 608 620 160 438

volved in the refining of petrochemicals and fuels in the pe- [http://dx.doi.org/10.1016/j.rser.2014.07.129]

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