Renewable and Sustainable Energy Reviews 88 (2018) 151–159

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Renewable and Sustainable Energy Reviews

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

Thermochemical conversion of sugar industry by-products to biofuels T

⁎
Thibault Nicodème, Thomas Berchem , Nicolas Jacquet, Aurore Richel
University of Liège, Gembloux Agro-Bio Tech, Laboratory of Biomass and Green Technologies, Passage des Déportés, 2, B-5030 Gembloux, Belgium

A R T I C LE I N FO A B S T R A C T

Keywords: Replacement of petroleum by other energy sources is one of the principal challenges of contemporary en-
Sugarcane bagasse gineering. One of the most promising substitutes for petroleum is biomass, chemically converted into fuel. For
Sugar beet pulp instance, as the world's biggest producer of sugarcane, Brazil generates large quantities of agricultural residues
Biofuel from sugarcane cultivation which could be used to produce biofuels for transportation and aviation (i.e. jet fuel)
Fischer-Tropsch
without much difficulty. Furthermore, sugar beet industry generates important amount of waste that could be
Gasification
Thermochemical pathway
valorized into biofuels. The purpose of this article is to review the different technologies currently available for
the production of biofuels via a thermochemical pathway using sugarcane bagasse and sugar beet pulp as
feedstock, with specific interest in using feedstock gasification and subsequent conversion of the synthetic gas
into fuel. Gasification is a longstanding process of conversion of carbonaceous material into a gaseous compound
(syngas) and a solid output, called char. Several kinds of gasifiers are described, as well as the syngas cleaning-up
process, and the characteristics of several processes through which syngas is converted into synthetic fuel are
detailed, including Fischer-Tropsch (FT), Methanol-to-gasoline (MTG), Methanol-to-olefins (MTO) as well as
pyrolysis.

1. Introduction
An important issue concerns the availability of fuels in the coming
years. Oil reserves depletion and scarcity of petroleum lead transport
industry to look after new fuels [1]. Moreover, petroleum is a great
contributor to CO2 emissions and thus is implicated in global warming
[2]. Those considerations about the non-renewable aspect of petroleum
are not recent. Indeed, in the early 1970, the Club of Rome expressed
concerns about an exponential growth of population combined with
finite hydrocarbon-based energy sources like petroleum [3]. So re-
placement of petroleum is one of the greatest challenge of the 21st
century. Solutions exist but assistance from governments is needed, for
example with financial contribution or by implementing policy that
supports biofuel technology and production [4].
Aviation industry has shown its determination to reduce its en-
vironmental impact. Therefore, aviation industry has engaged itself in
the ambitious challenges of being carbon neutral in 2020 and reducing
CO2 emissions to 50% of 2005 level in 2050. In order to achieve these
objectives, improvements are expected in several ways: more efficiency
of fuels with improved turbines, design of airplanes and advanced
airspaces management [5]. Biofuels can be another solution in order to
reduce CO2 emissions. Sustainable biofuels dedicated to aviation in-
dustry had to be “drop-in” fuels. “Drop-in” fuels define biofuel that,
when blended with conventional jet fuel up to a ratio defined by a fuel
specification, can use the same supply infrastructure and do not require
any adaptation of aircrafts or engines.
The production of biofuels can be divided into three generations.
This distinction is mainly based on the origin and the type of biomass
used to produce the biofuel.
First generation biofuels are elaborated typically from the storage
organs of the plants, containing mainly sugars, starch and oil. These
resources enable to produce biofuel through relatively cheap and rapid
techniques (microbial fermentation of carbohydrates and transester-
ification of oils) [6]. However, first generation biofuel is now com-
monly recognized as a threat for the food security since their devel-
opment could greatly influences the land use dedicated to a single
energetic use and, therefore, the world food prices. Then, it seems
difficult to conciliate the increasing demand of both food and biofuels
[7].
This review focuses on second generation biofuel, using byproducts
from agrofood industries, especially sugar industry (sugar beet pulp and
sugarcane bagasse). The use of such products allow to keep the first
purpose of the feedstocks in the human food sector, without inducing
any disruption in the cultures in term of land use or destabilization of
the market of the products that already exist.
The third generation relies on the algal biomass. Certain species of
microalgae’s can have a very high oil content that acts as the starting
compound for the fuel synthesis [8]. Microalgae’s show a rapid growth

⁎
Corresponding author.
E-mail addresses: thibault.nicodeme@ulg.ac.be (T. Nicodème), thomas.berchem@ulg.ac.be (T. Berchem), Nicolas.Jacquet@ulg.ac.be (N. Jacquet), A.Richel@ulg.ac.be (A. Richel).

https://doi.org/10.1016/j.rser.2018.02.037
Received 20 December 2016; Received in revised form 4 September 2017; Accepted 27 February 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
T. Nicodème et al.
rate and a high production capacity of lipids. They also do not compete
with food or feed production since they can be grown on non-arable
lands or in saline water. These advantages depict the third generation
biofuels as a complementary way of energy production to the second
generation rather than a competing technology.
1.1. Sugarcane and sugar beet industries
In the last decades, sugarcane culture has been largely developed in
Brazil for the production of sugar and bioethanol, but its potential is not
being fully realized. Indeed, the lignocellulosic wastes of the sugarcane
(i.e the bagasse and the straw) can successfully be converted into bio-
fuel since bagasse and the straw account for two third of the total en-
ergy of the plant [9].
Sugarcane cultivation is relevant especially to Brazil, which gen-
erates 670 million tons of sugarcane in 2015–2016, or one third of the
world’s total output [10]. After being processed, this crop yields almost
200 million tons of bagasse and 220 million tons of straw (wet basis)
per year as by-products [9]. For a long time, sugarcane bagasse has
been burnt to supply electricity to the factories and to the national grid.
Estimations show that currently almost 90% of bagasse from sugar
ethanol production plants are used to make electricity and heat by
cogeneration [11]. In 2008, about 3% of total electricity consumed in
Brazil came from this “bio-electricity” [12]. Moreover, from an en-
vironmental point of view, power generation is a key-element con-
sidering his high potential in CO2 emission reduction [13]. Sugarcane
wastes are also used in others applications such as pulp and paper in-
dustry, chemicals and metabolites (alcohols, enzymes) manufacturing.
In Brazil, roughly half of the sugarcane straw is left on the field to
prevent soil erosion, for the conservation of its agronomic character-
istics related to its chemical content (C, N, P, K, Ca, Mg and S) and for
the maintenance of soil microbiota [9]. The other half is either burned
to generate electricity or converted to metallurgical coke. In addition,
recent improvements of harvesting techniques provide large amount of
straw usable for co-generation or ethanol production [9].
The lignin, cellulose and hemicellulose contents of several bio-
masses are summarized in Table 1. Sugarcane bagasse is mainly com-
posed of cellulose (40–50%), hemicellulose (20–30%), lignin (20–25%)
and 2–4% ashes (dry basis) [14,15]. Ashes content is similar to sugar
beet pulp but is quite low compared with alfalfa, wheat straw or rice
husk with 7–9%, 7–10% and 15–20% respectively. Moreover, thanks to
its high crop yield (80 tons/ha/year), sugarcane is also considered as a
great solar energy reservoir compared with wheat (1 ton/ha/year) and
trees (20 tons/ha/year) [16–18]. Combustion and gasification of su-
garcane bagasse can be seen as carbon neutral processes because the
amount of CO2 generated is the same consumed during the plant
growth [15].
Sugar beet industry is well developed in Western Europe (France,
Germany and Belgium) with a production of about 190 million tons in
2014 [19]. Sugar refineries generate an important amount of by-pro-
ducts such as pulps, leaves and crowns. Beet pulp is the main waste
proceeded by this industry. Concretely, one ton of sugar beet gives more
or less 500 kg of pulp at 10% dry matter which is equivalent to 55 kg at
90% dry matter. Beet pulp is especially used to feed cattle but other
valorisation pathways exist. For example, sugar beet pulp is rich in
Table 1
Cellulose, hemicellulose, lignin and ashes content (referred on a dry basis) of different
biomasses [15, 17, 18].
Biomass type % Cellulose % Hemicellulose % Lignin
Sugarcane bagasse 40–50 20–30 20–25
Sugar beet pulp 20 32 1–2
Alfalfa 30 12–17 12–14
Wheat straw 34–40 21–26 11–23
Rice husk 40–50 20–25 25–30
Renewable and Sustainable Energy Reviews 88 (2018) 151–159
pectins that are used in cosmetic sector as surfactants. Pulp and paper
industry also uses compressed or dried beet pulp as an alternative
component. Lastly, this waste can be burned or spread on the fields. The
second interesting by-product of sugar beet industry is molasses. It is
used as fermentation medium for yeast or alcohol manufacturing. Fi-
nally, leaves and crown are also considered as cattle food [20].
Thanks to its appropriate climate and the quality of the soil,
Belgium is a favourable land to sugar beet culture. Indeed, in 2014,
sugar beet production has reached 5,121,524 tons leading to approxi-
mately 431,744 tons of crown and 281,684 tons of dehydrated pulps
[21]. The important amount of waste encourages researchers to focus
on the valorisation of pulp, leaves and crown by thermochemical
pathway. Beet pulp pyrolysis has for example already been investigated
[22,23].
Moreover, with the sugar quotas abolition in 2017, sugar beet in-
dustry will face economic challenges and shall find solutions to ensure a
financial sustainability of all sugar beet industry stakeholders. Biofuel
production from sugar beet waste could be a way of valorisation.
1.2. Bioethanol and “Proalcool” program
During the oil crisis of the 1970′s, Brazil’s government founded the
“ProAlcool” Program to develop ethanol production as an alternative to
fossil fuels [11]. Thanks to this program, Brazilian automotive market is
dominated by so-called flex-fuel cars which are able to run either on
gasoline, hydrated ethanol, or any proportional mixture of the two
fuels. The initial mandate of this program was to blend gasoline with
5% ethanol but has since increased to 22% [24]. Presently bioethanol is
blended in gasoline to a concentration of about 30% (v/v) of gasoline
and yet increasing demand is forecast for the next 10 years.
The hundred million tons of sugarcane bagasse harvested annually
and used for electricity generation seems to be the most promising
source of carbon to make cellulosic ethanol [11].
Initially bagasse was converted to ethanol biochemically, through
enzymatic hydrolysis and fermentation of sugar but recent work have
demonstrated that a thermochemical process (i.e. gasification followed by
the Fischer-Tropsch process) offers several advantages over the conven-
tional biochemical methods [25,26]. The thermochemical pathway de-
rives a greater benefit from economies of scale due to its large capital costs
and its capacity to process dry and compacted raw materials [27]. In order
to be economically competitive, an important point is the combined
generation of biofuel, electricity and specific chemicals. Combining gasi-
fication of biomass and the Fischer-Tropsch process is a promising way to
make biofuel and it deserves a special focus (Fig. 1).
This article is part of this approach and reviews the different ther-
mochemical conversion technologies currently available for the pro-
duction of biofuels using sugarcane bagasse and sugar beet pulp as
feedstock, with specific interest in using feedstock gasification and
subsequent conversion of the synthetic gas into fuel.
% Ashes
2–4
4–6
7–9
7–10
15–20
Fig. 1. Overview of biofuel production by thermochemical pathway.
152
T. Nicodème et al.
2. Gasification
Gasification is a chemical process for the conversion of carbonac-
eous materials of organic or fossil origin into syngas, a mixture com-
posed primarily of carbon monoxide and hydrogen along with small
amounts of carbon dioxide, methane and water [28]. Gasification is
achieved by heating the feedstock at temperatures above 700 °C with a
controlled flow of air or steam in an atmosphere so poor in oxygen that
combustion cannot occur. Gasification process is similar to pyrolysis,
except that the latter occurs in the complete absence of oxygen while
gasification tolerates the presence of oxygen in low concentration [29].
Syngas has many different applications: it can be used to make me-
thanol and hydrogen, or converted into synthetic fuel. In this instance,
the Fischer-Tropsch process is successfully used to convert syngas to
biofuel. The gasification had to be successfully performed to generate
an efficient syngas. Generally, sugarcane bagasse arrives at the bior-
efinery with a moisture content of 50% and a drying process is required
to lower it up to 20% before gasification [30].
2.1. Process
Gasification can be broken down into five consecutive stages (de-
hydration, pyrolysis, combustion, gasification, additional reactions)
characterized by the reactions which occur on the substrate. Several
parameters such as pressure, temperature, type of gasifier and feedstock
composition also influence the reactions taking place in the reactor.
2.1.1. Dehydration
The evaporation of the moisture of the biomass usually occurs
around 100 °C during the dehydration step. The thermal energy needed
for the evaporation comes from others steps of the process, in particular
oxidation. The steam generated by water vaporization can be blended
with gas flow and take part in subsequent chemical reactions, parti-
cularly the “water-gas shift reaction” if temperature is high enough
2.1.2. Pyrolysis
This step consists of a thermochemical degradation of the carbo-
naceous materials occurring between 250 and 700 °C. The cracking of
chemical bonds occurs and low molecular weight compounds are cre-
ated from the initial organic material. Endothermicity of pyrolysis re-
action (Reaction 1) required heat that provides from the oxidation step.
Biomass  ↔   H2 + CO + CO2 + CH4 + H2 O (g )  +  Tar
+ Char ∆H > 0 (1)
The gaseous fraction is a blend of gases (H2, CO, CO2 and light
hydrocarbons) that are incondensable at ambient temperature, re-
presenting 70–90 wt%. In addition to gas, a solid and a liquid fractions
are also obtained. The residual solid is referred as char and the quantity
can range from 5 to 10 wt% to 20–25 wt% for fluidized-bed gasifiers
and fixed-bed gasifiers respectively [31,32]. Its structure and compo-
sition is a function of the chemical composition of the feedstock. The
amount of tars (i.e. liquid fraction) also depends of the gasifier and it’s
constituted of complex organics compounds that can be condensed at
low temperature.
2.1.3. Oxidation
The low-oxygen atmosphere reacts with volatile compounds re-
leased during pyrolysis as well as a part of the char to generate carbon
dioxide (Reaction 2), a small amount of carbon monoxide (Reaction 3).
Hydrogen combustion also occurs and it creates water (Reaction 4). The
three reactions are exothermic and thus it provides the thermal energy
required to sustain the gasification process.
C + O2  →   CO2 ΔH = −394 kJ / mol Char combustion (2)
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Renewable and Sustainable Energy Reviews 88 (2018) 151–159
1
C+ O2  →   CO ΔH = −111 kJ /mol Partial oxidation
2 (3)
1
H2 + O2  →   H2 O ΔH = −242 kJ / mol Hydrogen combustion
2 (4)
CO2, CO and water are the main gaseous compounds yielded during
this step as well as thermal energy required for the entire process. If
pure oxygen is used as oxidant agent, nitrogen is practically absent of
the gaseous mixture. On the contrary, if air is used for biomass oxida-
tion, nitrogen can been found and, in the end, contributes to dilute
syngas.
2.1.4. Reduction
During the reduction step, the gas mixture and the char, generated
during the pyrolysis and oxidation steps, react each other in order to
obtain the final syngas. Carbon in the char reacts with steam to produce
carbon monoxide and hydrogen, according to Reaction 5.
C + H2 O  ↔   CO + H2 ΔH = 131 kJ /mol Reforming of the char (5)
Reactions 6, 7 and 8 also occur during the reduction step:
C + CO2  ↔ 2CO ΔH = 172 kJ /mol Boudouard reaction (6)
C + 2H2  ↔   CH4 ΔH = −75 kJ /mol Methanation reaction (7)
CO + H2 O  ↔   CO2 + H2 ΔH = −41 kJ /mol Water gas shift reaction
(8)
Franco et al. [33] showed that in the range of temperature of
730–830 °C, besides the reforming and cracking reactions, the water gas
shift reaction is the most influent for the final syngas composition. The
[CO]/[CO2] ratio of the syngas is determined by both the Boudouard
and the water gas shift reactions. The generation of CO2 by the water
gas shift reaction increases up to 830 °C. At higher temperatures, CO2
concentration decreases due to reactions consuming CO2 like Bou-
douard reaction.
The exothermicity of Reactions 7 and 8 does not provide enough
heat required for Reactions 5 and 6. The energy needed comes from the
oxidation reactions.
2.1.5. Water-gas shift and steam-methane reforming
In the case of a high carbon conversion, heterogeneous Reactions (5,
6, and 7) are supplanted by water-gas shift (Reaction 8) and steam-
methane reformation (Reaction 9). These homogeneous gas phase re-
actions play an important role in determining the final syngas compo-
sition.
CH4 + H2 O ↔ CO + 3H2 ΔH = 206 kJ /mol Steam methane reforming reaction
(9)
During gasification, the sulphur in the feedstock is converted to
hydrogen sulphide (H2S) as the major component along with a small
amount of carbonyl sulphide (OCS), while nitrogen is converted to ni-
trogen gas (N2), along with smaller quantities of amide (NH3) and hy-
drogen isocyanide (HCN). Trace elements including mercury, arsenic
and other heavy metals are mainly recovered in the ash and slag frac-
tions, although a small amount exists in the gaseous phase and must be
removed from the syngas before use.
Gasification is able to process a wide variety of feedstock having a
wide range of size, shape, bulk density, water content, energy value and
chemical composition such as wood (chips, pellets), plastics, alumi-
nium, municipal solid waste, industrial and agricultural waste and
wastewater.
2.2. Types of gasifier
A number of different configurations of gasifiers exists, including
fixed bed, fluidized bed and entrained-flow (or slurry) reactors.
Differences of gasification reactors relate to the way of contact between
T. Nicodème et al.
Fig. 2. Industrial gasifier. (A) Fixed bed gasifier; (B) Fluidised bed gasifier; (C) Entrained bed gasifier.
Electric Power Research Institute
the feedstock and the gasifying agent, the mode of heat transfer and the
residence time of the feedstock in the gasifier (Fig. 2).
2.2.1. Crosscurrent fixed bed ("updraft") gasifier
Oxidant agent flows up in crosscurrent through a fixed bed of coal
or biomass particles. The gasifier consists of a drying zone at the top,
followed by carbonization and gasification zones below. Combustion of
the feedstock takes place at the bottom of the gasifier. This kind of
gasifier requires a fuel with high mechanical strength and which is
resistant to caking in order to remain sufficiently porous. A weak point
of updraft gasifiers is the relative low throughput of the syngas.
2.2.2. Co-current fixed bed ("downdraft") gasifier
This gasifier is similar to the updraft gasifier, except that the oxidant
agent and the carburant flow in co-current. Heat must be added to the
top of the bed either by burning a small quantity of carburant, by using
an external heat source or by recovering heat from the exhaust stream.
Downdraft gasifier exhaust is relatively hot, so heat is commonly re-
covered and transmitted to the top of the bed. The energy efficiency of
this reactor is similar to that of a counter-current gasifier with the
added benefit of having less tar entrained in the outlet stream, because
the co-current configuration ensures that entrained tar particles must
pass through a region of hot char before escaping the reactor.
2.2.3. Fluidized bed gasifier
In this reactor, fuel particles are fluidized by the oxidant agent
coming from the bottom of the reactor. In the case of fluidized gasifier,
the feedstock behaviour is similar to a liquid. Fuel particles are mixed
and suspended by gas bubbles and that allows a great exchange of
matter and heat between gas and solid particles. Ashes are removed dry
or form heavy aggregates that fall to the bottom of the reactor.
Fluidized bed gasifiers are particularly useful for fuels generating large
quantities of corrosive ashes that would damage the walls of the re-
actor. Biomass fuels are known to generate such corrosives ashes.
Thanks to its high mixing capacity and its high heat and mass transfer
that allow a homogeneity of temperature in the gasifier, fluidized bed
gasifier seems the most promising reactor for biomass gasification.
2.2.4. Entrained-flow gasifier
In an entrained-flow gasifier, atomized droplets or dry pulverized
solid are fed in co-current with the oxidant. The filling of the reactor
with water slurries or dry feed is an easy operation but the introduced
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Renewable and Sustainable Energy Reviews 88 (2018) 151–159
water has to be evaporated during the drying step. A high temperature
(1300–1500 °C) and pressure (25–30 bars) gasification take place in a
dense cloud of droplets. Small particle size allows gasification to occur
relatively quickly, permitting residence times of a few seconds with
high carbon conversion efficiency [34]. The high temperature of en-
trained-flow gasifiers also melts coal ash into vitreous inert slag. That is
easily disposed. Environmentally speaking, entrained-flow gasifier is
the most benign. Indeed, the obtained syngas is mainly composed of H2,
CO and CO2, with trace amount of contaminants that are easily re-
moved downstream of the reactor.
2.2.5. Plasma gasifier
Alongside solid, liquid and gas, plasma is the fourth state of matter.
Plasma state appears when a gas is heated at very high temperature
(10,000 °C) and becomes highly ionized and thus is able to conduct
electricity. Those high temperatures are obtained thanks to an electric
arc created between two electrodes. Since 30 years, the Westinghouse
Plasma Corporation developed the plasma technology for the treatment
of municipal solid waste. High temperature of the plasma allows an
important degradation of the feedstock nearly up their elemental form
[35]. An interesting advantage of plasma high temperature is the de-
gradation of toxic compounds into safe elements.
2.3. Syngas cleaning system
Upon leaving the gasifier, syngas generally carries a range of im-
purities including particulates (soot, polycyclic aromatic hydrocarbon,
ash forming compounds) and undesirable gas components like acid
gases (H2S, COS, CO2) [36]. Downstream processes often require spe-
cific syngas composition characteristics. In the case of synthetic fuel
production, the CO2, hydrocarbons, nitrogen and water vapour contents
must be below a given threshold. In particular, the Fischer-Tropsch
process catalyst requires a specific gas to carbon dioxide ratio (H2/CO),
specifically 0.6 for iron catalysts and 2.0 for cobalt. The water-gas shift
reaction (Reaction 8) allows the conversion of carbon monoxide of the
syngas into hydrogen. Depending on whether this reaction occurs be-
fore or after the removal of sulphur from syngas, it is called sweet or
sour-gas shift reaction respectively [36].
Particles are removed from syngas through a water wash consisting
of two steps: a quench pipe (i.e. carbon separator) and a packed tower
(i.e. carbon scrubber). The quench pipe unit consists of directly
spraying water which removes 95% of carbon while the scrubber passes
T. Nicodème et al. Renewable and Sustainable Energy Reviews 88 (2018) 151–159

Fig. 3. Fluidised bed Fischer-Tropsch reactors. (A) CFB reactor; (B) FFB reactor; (C) slurry phase bed reactor. Note the scale of the reactor is not respected. CFB reactor being about three
times higher than FFB and slurry phase bed reactor.

water in counter-current to the gas in two packed beds [36]. Two
pathways of syngas cleaning can be distinguished: the conventional
“wet” low temperature cleaning and the advanced “dry” hot gas
cleaning. Recently hot gas filter have been developed for efficient
particulate separation. In the “hot gas cleaning” process, high tem-
perature syngas passes through several filters and separation units. This
process is interesting when preceded by a reformer or shift reactor,
because these steps have high inlet temperature [37]. Hot gas cleaning
is still in development in several universities and thus not commercially
available at the moment.
Liquid selectivity is determined by the "chain growth probability”,
meaning the likelihood that a growing hydrocarbon chain will add
another monomer rather than terminating. High liquid selectivity is
required to form long hydrocarbon chains with more than five carbon
atoms (i.e. C5+). The Anderson-Schulz-Flory (AFL) distribution de-
scribes the relationship between chain growth probability and liquid
selectivity [37]. The AFL distribution is given by the Eq. (12), where n
is the length of the hydrocarbon:
Cn = ∝n −1 (1 − ∝) (12)

Where α is the chain growth probability and (1 - α) is therefore the

3. Fischer-Tropsch
probability that the chain growth terminates. Several parameters in-
fluence liquid selectivity including: the type, composition, supporting
Thanks to its chemical composition, syngas has many applications.
substrate, preparation and age of the catalyst; the temperature and
In 2006, the highest-volume use of syngas was in the synthesis of am-
pressure; the reactor dynamics; the [H2]-to-[CO] ratio.
monia, followed by its use as a source of hydrogen gas in the oil refining
Undesirable reactions like methanation, the Boudouard reaction,
process and as a precursor in the production of methanol [38]. How-
coke deposition, oxidation of the catalyst or carbide formation can also
ever, by 2040 the main sectors of demand for syngas are projected to be
occur. Those undesirable reactions are avoided by choosing the right
fuel and renewable chemical manufacturing. Syngas is also used in heat
operating conditions [39].
and power generation but also (bio) fuel production. Syngas is already
Different kind of catalysts exist for Fischer-Tropsch synthesis, the
used to generate fuel but will become increasingly important thanks to
most commonly of which are composed of iron and cobalt. Cobalt
Gas-to-Liquid (GTL) processes including the Fischer-Tropsch and me-
catalysts are selected for their higher turnover rate, longer life and re-
thanol-to-gasoline processes producing diesel and gasoline from bio-
duced generation of unsaturated hydrocarbons (olefins) compared with
mass [38].
iron catalysts. Those catalysts have a high tolerance for sulphur, are
The Fischer-Tropsch process (referred to here as FT) was developed
cheaper, produce more olefins and alcohols but their lifetime is short
in the 1920s in Germany and used during World War II to generate
[40].
synthetic transportation fuels from coal. In a classic catalytic Fischer-
Exothermic reactions of the Fischer-Tropsch process provide a lot of
Tropsch synthesis, one mole of carbon monoxide reacts with two moles
heat that has to be removed in order to avoid a deactivation of the
of hydrogen gas to mainly yield long straight chain of hydrocarbons
catalyst due to sintering and fouling. Fischer-Tropsch reactors are thus
(CxH2x) and a minority of branched hydrocarbons (Reaction 11).
designed to favour heat exchange and it is possible to distinguish three
CO+2H2→−(CH2) − + H2 O (11) types: fluidized bed reactors, fixed bed reactors and slurry phase re-
actors. Several Fischer-Tropsch reactors using the fluidized bed tech-
Here, (─ CH2 ─) represents a methylene monomer in a longer alkyl
nology can be cited: circulating fluidized bed (CFB), fixed fluidized bed
chain.
(FFB) and slurry phase bubbling reactors (Fig. 3) [37].
Typical operating temperature and pressure for Fischer-Tropsch
Fischer-Tropsch synthesis requires a H2/CO molar ratio of 2:1. In
synthesis are between 200 and 350 °C and 25–60 bars. Those operating
comparison with coal gasification, biomass gasification lead to a lower
parameters produce a broad distribution of hydrocarbons ranging from
H2/CO molar ratio in the feed gas which needs to be increased thanks to
light synthetic crude oil (syncrude), light olefins to heavy waxy hy-
water-gas shift reaction. This last reaction is accelerated by iron cata-
drocarbons. Hydrocracking or isomerization of syncrude leads to great
lysts, which is a feature that make them preferable to cobalt catalysts
diesel fuel, lube oils or naphtha, which is an ideal feedstock for cracking
thus those are favoured for Fischer-Tropsch reformulation of gasified
to olefins [38]. In order to directly create gasoline and light olefins,
biomass [37].
higher temperature from 330° to 350 °C are required. On the contrary,
After Fischer-Tropsch process, a hydrocracking step can be per-
ideal temperature for the production of waxes and diesel ranges from
formed if diesel is the desired final compound. Hydrocracking combines
220° to 250 °C.
H2 with alkenes to form unsaturated hydrocarbons.
The performance of a FT process relies on the liquid selectivity.

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T. Nicodème et al.
4. Methanol production
Methanol is a molecule with many applications – it can be used as a
transportation fuel, either pure or blended with other hydrocarbons and
also used for the production of synthetic gasoline and olefins. Two re-
actions occur simultaneously in methanol synthesis reactor. On one
hand, the water-gas shift (WGS) reaction generates CO2 and H2 and on
the other hand, carbon monoxide and hydrogen reacts to give methanol
according the Reaction 13. This reaction is highly exothermic and so it
can be used to preheat the inlet flow of syngas or generate high-pres-
sure steam [41].
CO  + 2H2 ↔ CH3 OH (13)
CO + H2 ↔ CO2 + H2 (14)
The CO2 content of the syngas used in the methanol synthesis re-
actor has a significant influence on the composition of the effluent
leaving the reactor. According to Reaction 14, an increase of CO2
concentration drives the water-gas shift reaction equilibrium towards
reactants, meaning towards increased water concentration [42].
Because the water-gas shift is exothermic, conversion of CO and H2
to methanol is favoured at low temperature although this also decreases
the reaction rate in accordance with Arrhenius law. Pressure also affects
the equilibrium of the reaction with increasing pressure favouring
methanol production. Operating temperature and pressure in the re-
actor ranges between 220 and 275 °C and 50 and 100 bars respectively.
Catalysts used for methanol synthesis are composed of copper, zinc
oxide and alumina. Methanol can be the starting molecule for two other
reactions to yield dimethyl ether (DME) and hydrocarbons.
In the 1970′s, MOBIL developed the MTG (Methanol-to-Gasoline)
and the MTO (Methanol-to-Olefins) processes in order to convert me-
thanol into gasoline and methanol into olefins respectively. The key
element of the processes is the zeolite catalyst ZSM-5 which converts
methanol to hydrocarbon chains.
In the MTG process, methanol is vaporized in heat exchangers op-
erating at temperature between 300 and 320 °C. Methanol vapours then
pass to the dimethyl ether reactor in which a chemical equilibrium is
reached methanol, DME and water in accordance with Reaction 15.
2CH3 OH ↔ CH3 OCH3 + H2 O (15)
This exothermic reaction is generally run at 400–420 °C and about
75% of methanol is converted into DME and water. The DME-water
mixture is blended with recycle gas that is send to the conversion re-
actors containing the ZSM-5 catalyst. Recycle gas (mainly composed of
light hydrocarbons, CO2 and H2) is used to absorb excess heat generated
during the reaction. DME is then converted into light alkenes thanks to
ZSM-5 catalyst. Cyclisation and polymerisation of those alkenes give
the final products with about 80% of alkyl chains containing at least 5
carbon atoms [41,42].
The MTO reactor operates between 375 and 400 °C and at 1–1,2 bar.
100% of methanol is mainly converted into olefins (56.4%), gasoline
(35.7%), paraffins (6.5%). The mixture is fractionated in a separator
unit where 100% the olefins are directly sent to the ZSM-5 catalyst
reactor while 100% of the C1-C3 paraffins are recycled back to the MTO
reactor. The ZSM-5 catalyst allows the conversion of olefins into ga-
soline and a distillate at a ratio gasoline/distillate ranging from 0.12 to
100. Finally, the products are sent to another separator unit that gives a
diesel and a kerosene fraction.
5. Pyrolysis
Biomass pyrolysis is another thermochemical process through which
biofuels can be obtained. Pyrolysis is defined as the thermal degrada-
tion of carbonaceous material in total absence of oxygen or with a very
few amount of oxygen preventing gasification conditions [14]. Similar
to gasification, pyrolysis produces a gas mainly composed of CO, H2,
156
Renewable and Sustainable Energy Reviews 88 (2018) 151–159
CO2, CH4 and short-chain hydrocarbons. A part of this gas can be
condensed into the so-called pyrolytic liquid. Finally, pyrolysis also
provides a solid part called the char. This liquid, also called bio-crude
oil, has several uses but above all can be used as fuel. Two kinds of
pyrolysis can be distinguished, namely fast and vacuum pyrolysis. Fast
pyrolysis is designed to maximize liquid yield with several parameters
such as high heating rates, an operating temperature of 500 °C, a re-
sidence time of 2 s and a quick cooling of the vapour [2,43]. While
vacuum pyrolysis has an operating temperature of 300 °C, promotes a
high char yield and is more expensive than fast pyrolysis. Heating value
of the bio-oil produced only represents 50% of conventional fuel oil
[44].
The pyrolysis of lignocellulosic biomass is complicated by the fact
that cellulose, hemicellulose and lignin pyrolysis through different
mechanisms and at different temperatures. Cellulose is generally the
main component of bio-oil whereas lignin is mainly found in the char. A
widely accepted model for cellulose pyrolysis was developed in the
1970′s by Broido and Shafizadeh. This model assumes that, at high
temperatures, cellulose reacts to form a so-called “active cellulose” [45]
which then decomposes through to two competing reactions forming
volatiles molecules and solid intermediates respectively. Despite being
largely accepted, the model has been neither corroborated experimen-
tally [46].
At present, two disadvantages of bio-oil obtained by pyrolysis are its
physico-chemical instability leading to storage difficulties and the lack
of a reliable framework to determine the quality of bio-oil [2]. More-
over analysis performed on pyrolysis oil from biomass showed a che-
mical instability and was a highly oxygenated and complex oil. An
upgrading of the liquid oil is thus achieved by reducing oxygen content
and residues elimination [47].
6. Recent developments
Ahmed and Gupta (2012) studied the influence of the temperature,
during steam gasification of sugarcane bagasse, on the chemical com-
position of the syngas. Steam temperatures of 800, 900 and 1000 °C
were investigated in a semi-batch reactor. An increase of gasification
temperature led to several modifications such as an increase in CO flow
and a decrease in CO2 flow. The CO/CO2 ratio was higher at 1000 °C
than at lower temperatures which means a higher quality syngas [15].
In 2017, Varma and Mondal [48] conducted pyrolysis of sugarcane
bagasse in a semi batch reactor to study the effect of temperature,
heating rate, biomass particle size and nitrogen flow rate on the pyr-
olysis product yields. Results show that temperature of 500 °C, heating
rate of 50 °C/min, particle size of 0.5–0.6 mm and nitrogen flow rate of
100 cm3/min conducted to obtain bio-oil potentially valuable as a re-
newable fuel with a maximum yield of 45.23 wt%. Montoya et al. [49]
show also than effect of heating rate on the yield of fragmentation and
dehydration products is only important till 100 °C/s and that no sig-
nificant changes in product yields are observed at higher heating rates.
The study of Figueroa et al. [29] focused on the comparison of
pyrolysis and gasification of sugarcane bagasse in a fixed bed reactor.
The amount of char, tar and gas produced were evaluated as well as the
composition of the syngas. Results showed that more gas is produced
when pyrolysis temperature increases. The authors concluded that the
pyrolysis process had to be improved because the gas yield was too low.
Sugarcane bagasse gasification at 900 °C produced greater amount of
gas compared to pyrolysis, 66–53% respectively. Results showed that
varying the reaction time (from 20 to 180 min) had no influence on the
CO2 and CH4 content. At the contrary, by extending the reaction time,
an increase in H2 and a decrease in CO contents can be observed,
mainly explained by the water-gas shift reaction [16].
The research of Sheikhdavoodi et al. [50] concerned the gasification
of sugarcane in supercritical water with catalyst in order to maximize
H2 production. Two advantages of supercritical water gasification is the
high reaction efficiency and the H2 selectivity. The effect of different
T. Nicodème et al.
catalysts was investigated (five alkali salts, Raney Nickel and activated
carbon) as well as temperature (400–800 °C). Different parameters were
evaluated: composition and gas yield, gas heating value, carbon gasi-
fication efficiency and hydrogen gasification efficiency. The authors
found that a temperature increase improves hydrogen yield. Moreover,
the highest hydrogen yield was obtained at 800 °C with the use of KOH
as catalyst.
The publication of Tavasoli et al. [51] talks about supercritical
water gasification in order to optimize the hydrogen production. The
gasification is performed by means of potassium and copper nanoca-
talysts supported on alumina in order to increase the selectivity towards
hydrogen production. By acting as a gasifier agent, Cu increases the
total amount of gases produced. At the contrary, the addition of po-
tassium to the catalyst leads to a diminution of H2, CO2 and the amount
of total gases. The authors showed that it is due to a negative effect of
potassium on the water-gas shift reaction. The maximal production of
H2 during gasification of sugarcane bagasse was achieved using the
catalyst with 20% copper and 2.5% potassium on γ-Al2O3.
Aho et al. [23] studied the pyrolysis in a fluidized bed reactor of two
kind of sugar beet pulps (pulp from sucrose extraction industry and
pulp after pectin extraction). They observed that the total amount of
char and water decreases and the amount of gas increases when the
temperature of pyrolysis increases. The pyrolysis oil is composed of
many oxygenated compounds but also contains about 28% of uni-
dentified components. Finally, the authors found that the chemical
composition of pulps bio-oil depends on the chemical composition of
the raw material.
The objective of the research of Yilgin et al. [22] was to study the
behaviour of pellets of lignite and sugar beet pulp alone and in a 50/50
(wt/wt) ratio. At 600 °C, flash pyrolysis of sugar beet pulp yielded much
more bio-oil and gas and fewer char compared with lignite. The ex-
planation is the difference of chemical composition between lignite and
sugar beet pulp. For example, carbon and oxygen content of lignite and
sugar beet pulp were significantly different: C: 66% and O: 28% (wt.)
and C: 43 and O: 49% (wt.) respectively. Moreover, there is a great
agreement between values obtained by experiments and by calculation
for the 50/50 blend of lignite and sugar beet pulp. It means that both
raw material do not interact with each other during pyrolysis.
In 2007, Devrim [52] studied the pyrolysis kinetics of several blends
of lignite and sugar beet pulp. Practically, thermogravimetric analysis
were performed and a kinetic model was established.
Recent study has been also published on the catalytic pyrolysis of
sugarcane bagasse to improve the quality of the liquid product from fast
pyrolysis. Mendes et al. [53] showed that gas yields increased with
temperature and the presence of ZSM-5 contributed to greater quan-
tities of gaseous deoxygenation products. Catalytic pyrolysis with ZSM-
5 generated also a significantly greater amount of valuable aromatic
compounds, such as toluene and C2-benzene isomers (xylenes and
ethyl-benzene), which are petrochemical intermediates with high
added values. Fast pyrolysis of sugarcane bagasse over sodium-based
catalysts was studied in a fixed-bed reactor at 500 °C by Nguyen et al.
[54]. Results showed that sodium concentration played a bigger role
than the surface area and porosity in the catalytic performance of
Na2CO3/γ-Al2O3 materials. On the other hand, Na2CO3/γ-Al2O3 catalyst
was shown to possess deoxygenation activity comparable to HZSM-5.
David et al. [55] showed also that sugarcane bagasse thermo-
chemical conversion to pyrolytic sugars production was improved by
HNO3 washing, followed by H2SO4 concentration of 0.2 wt% at 350 °C.
Results showed an increase in levoglucosan yield between 5 and 7 times
the yield obtained with raw bagasse.
In 2016, Goncalves et al. [56] investigated the production of bio-oil
from sugarcane bagasse and molasses using pyrolysis and CO2 activa-
tion. The process yield developed by authors reached 41.11% and bio-
oil obtained has similar properties and characteristics than proposed
specifications of the various grades of pyrolysis oils that could find
potential application as fuel or source of a number of valuable
157
Renewable and Sustainable Energy Reviews 88 (2018) 151–159
chemicals.
At last, literature showed that pre-processing methods that can be
applied to bagasse to make it a suitable feedstock for energy production
in thermochemical conversion systems. Anukam et al. showed that
torrefaction appears to be a better method than other pre-processing
methods (size reduction, drying, pelletising, briquetting) because its
only disadvantage (low volumetric energy density) can be balanced
easily by densifying the torrefied material [57]. Low power consump-
tion of torrefaction also makes it a better choice for sugarcane bagasse
pre-processing compared to other pre-processing methods.
It is interesting to note that at this day, no research has been per-
formed on gasification of sugar beet pulp and very few on pyrolysis. It is
probably due to the existence of others promising pathways of valor-
isation of sugar beet residues and the seasonality effect of sugar beet
culture.
7. Competing technologies
It is worth noting that thermochemical conversion of biomass to
biofuel competes with other ways of production of bioenergy such as
biochemical conversion processes and cogeneration. Sugarcane bagasse
is, for instance, considered as a strategic resource for the Brazilian
electrical system. Bagasse acts as a seasonal complement to hydro-
electricity [58]. The harvest of sugarcane occurs during the period of
low water inflows and therefore, enables to keep a constant production
of bioelectricity via cogeneration. Sugarcane industry is currently the
third most important energy source in Brazil, just after fossil fuels and
hydropower.
Biochemical conversion of biomass to second generation bioethanol
is an important stakeholder of the sugarcane industry as well.
Bioethanol sector is currently facing an increasing demand for anhy-
drous ethanol especially due to the policy adopted in several countries
worldwide to raise the proportion of bioethanol mixed in gasoline.
Cellulosic bioethanol is currently produced via various methods of
lignocellulosic pretreatment combined to enzymatic hydrolysis and
microbial fermentation.
In 2010, Anex et al. performed a techno-economic comparison be-
tween thermochemical and biochemical production of biofuels [59].
They established several scenarios with the technologies that are sui-
table for industrial application in the near future and that produce
“drop-in” biofuels from corn straw as single available biomass. Their
study highlighted considerable difference between pyrolysis, gasifica-
tion and biochemical conversion in both capital and operating costs.
One of the scenario involving the pyrolysis turned out to be the one
having the lowest capital cost while pyrolysis is the technology with the
lowest operating cost as well. On the contrary, the highest capital cost
was reached by a scenario involving the gasification. The biochemical
conversion showed the highest operating cost. Moreover, Daystar et al.
[60] have demonstrated that ethanol production using thermochemical
process lead to lower greenhouse gases emission than the biochemical
conversion process. On one hand, thermochemical process consumes
less process chemicals, and on the other hand, it has shown higher
amount carbon efficiency, meaning that a higher amount of carbon
remains in the products and less CO2 is emitted than during the bio-
chemical process.
8. Conclusion
Sugarcane bagasse and sugar beet pulp are very abundant biomasses
that can be effectively converted into biofuels. This review has depicted
the thermochemical pathway as a viable economic and ecological route
for the synthesis of second generation biofuels.
The review of the different thermochemical conversion technologies
for the production of biofuels, as presented in this paper, allows to
highlight the importance of the gasification step since syngas compo-
sition will influence Fischer-Tropsch reaction. It should also be noted
T. Nicodème et al.
that syngas composition depends on several parameters such as biomass
composition, type of gasifier process and operating temperature. In
comparison with Fischer-Tropsch, both methanol to-gasoline (MTG)
and methanol-to-olefins (MTO) processes require one additional step.
Pyrolysis is a process able to produce biofuels but it is clearly not the
most efficient. Moreover, MTG, MTO and pyrolysis present several
drawbacks compared with Fischer-Tropsch process.
The production of biofuels via gasification of sugarcane bagasse
follow by the Fischer-Tropsch process is pertinent. Indeed, the amount
of raw material, the requirements of aviation market and the experience
of sugarcane bagasse processing are three key factors. On the contrary,
sugar beet pulp does not seem to be an interesting raw material for the
production of biofuel. Although the available quantity is high, sugar
beet pulp is already used to feed cattle. Moreover, its chemical content
is more diversified and therefore more interesting for biotechnology.
High value added pathways has to be favoured rather than biofuel
production in the case of sugar beet pulp.
Acknowledgments
This research was supported by the European Union and the
Walloon Region with the European Funds for Regional Development
2014-2020 in the framework of the VERDIR Tropical Plant Factory
program (project BioResidus) (Form number : 814687-481490)
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