Review

Cite This: Energy Fuels XXXX, XXX, XXX−XXX pubs.acs.org/EF

A Combined Overview of Combustion, Pyrolysis, and Gasification of

Biomass
Ali Akhtar,* Vladimir Krepl, and Tatiana Ivanova
Department of Sustainable Technologies, Faculty of Tropical AgriSciences, Czech University of Life Sciences Prague, Czech
Republic

ABSTRACT: From the conventional use of biomass in the form of heating to the modern day use of biomass in the form of
electricity generation and biofuel production, biomass has always been part of the evolution of mankind. Modern day use of
biomass is gradually becoming more complex, and engineering played an important role in defining different directions. This
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review provides an overall view of biomass utilization through thermal treatment including combustion, pyrolysis, and
gasification. Efficient use of biomass with the desired output and minimizing the drawbacks are the core of the research, and
marginal focus is being held on developing new techniques. The variety of composition and uptake of different elements
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throughout the lifespan of biomass produces a mixture of results. In general, it can be seen that the optimization was observed
either in the form of chemical looping combustion to prevent greenhouse gas emission or in upgrading of bio-oil to produce
biofuels. The significant factor is the reaction conditions, which define the ultimate product yield and the products’ performance
in different applications. Moreover, the development of new systems is desired in the present scenario due to the limited
possibility of further improvement in the current systems.

1. INTRODUCTION products, however, researchers proposed different measures

Sustainability consideration in modern projects is an essential
criterion in the developed world and getting recognition day by
day in the developing world as well. It is not only the need of
the hour from an environmental point of view but also
economically suitable for handling large projects on a
commercial scale. “Sustainability of any product can be defined
by its level of carbon footprint, and reduction of this footprint
can be achieved by a change of built-in or external
characteristics which can also lead to a change of its
configuration.”1 One of the paramount issues in sustainability
is reducing the reliability on fossil fuels for energy generation
and chemical extraction on a daily basis. There have been
many routes being researched to focus on the alternative
sources of energy which not only reduce environmental
pollution but are also available recurrently. These sources are
also called renewable sources of energy and fuels. Solar, wind,
and biomass are some of the few emerging sources in this
scenario, where their availability throughout the world and
potential to cope with environmental pollution makes them the
most studied areas so far in this category.
Although the importance of each of the energy sources
cannot be denied, however, biomass contains significant value.
This can be due to its highly versatile composition, availability,
and conversion into many useful products depending on the
technology and conversion pathway. Biomass has a notable
advantage in terms of its ability to produce different chemicals
that can be modified according to the employed route for
processing of the biomass that is absent in other sources of
energy. Biomass can be utilized through combustion, 2
thermochemical3,4 and biochemical5 treatment technologies
producing energy, biofuels, and biochemicals accordingly.
Figure 1 explains the different treatment technology pathways
to obtain desired products. Although all the processing
techniques contain some form of drawback in their end
and procedures to improve the properties, for instance, using
reduced pressurized distillation to improve heating values and
reduce corrosivity of the bio-oil produced through pyrolysis6
and changing fatty ester composition through different ways in
biodiesel production from vegetable oil and animal fats.7 Each
of the processes has been reported extensively in the past
decade, and major breakthroughs have been observed, moving
from first generation biofuel to fourth generation biofuels. The
production of fuels and chemicals through waste sources to
energy specific crops and genetically modified crops has
reached its peak, and the next pathways must be explored to
improve the efficiency of these processes. Multiple process
integration of biofuel and energy production with cost
optimization must be the focus of future studies to employ
these processes on an industrial scale.8 This study focuses on
the recent advances in biomass-based renewable energy and
fuel from the perspective of each of the processing
technologies, including combustion, pyrolysis, and gasification,
and provides an overall background in this area.
2. COMBUSTION
2.1. Biomass Components. Biomass primarily consists of
three main components, (i) cellulose, (ii) hemicellulose, and
(iii) lignin, and three minor components, (iv) proteins, (v)
sugars, and aliphatic acids, and (vi) fats. They have different
combustion behaviors and degradation patterns and release
energy according to the type of biomass and its composition.
Cellulose is glucose monomers attached to each other through
straight link chains in β crystalline form (unchained polymer).
Received: May 13, 2018
Revised: June 18, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.energyfuels.8b01678

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Figure 1. Biomass processing technologies and respective products obtained through each of the technologies.
Hemicellulose, on the other hand, contains sugar monomers
which are amorphous in nature and is a branched polymer.
Lignin holds phenyl propane units with biopolymers9 and
works as a glue to hold the fibers of the cellulose. This ability
gives the lignin a very prominent place in the field of
biochemicals and exhibits versatility. The chemical structure of
cellulose, hemicellulose, and structural units found in lignin
can be seen in Figure 2. All the components of the biomass
contain different reaction behaviors upon degradation into
different chemicals, which makes it arduous material to deal
with; however, this ability holds an advantage in terms of
segregation. Conversion of cellulose into other valuable
products through degradation is considered to be a strenuous
job compared to the rest of the composition.9 The variation of
each of the components in hard wood and soft wood biomass
is given in Table 1. It can be seen that the major difference lies
in lignin concentration of both types of biomass, where soft
wood contains higher lignin content than hard wood. Flax and
hemp contain a significantly higher concentration of cellulose
and subsequently lower concentration of lignin. Low lignin
content fibers prolong the burning, which leads to incomplete
combustion and lower heat evolved,10 hence not being suitable
for energy and heat production. Lignin content also
significantly affects the activation energy of particular
biomasses. They might be suitable in construction applications
as so-called composites or fiber reinforced concrete as heat
resistant materials.
2.2. CO2 Emissions. Biomass, a renewable source of
energy, produces net zero CO2 emissions upon its combustion
into boilers and reactors for energy and heat production. Co-
firing of the biomass with coal can reduce the greenhouse gas
emission significantly while maintaining a consistent supply of
renewable feedstock.11 Carbon capture and storage integration
into the combustion plant can significantly enhance the
environmental potential; however, the energy consumption is
the main barrier in this scenario with a decrease in efficiency.
B DOI: 10.1021/acs.energyfuels.8b01678
Review
Lopez et al.12 reported a techno-economic analysis of coal
biomass cocombustion for up-scale power plants. It was found
that a 300 MW power plant with 40−50% biomass
cocombustion was a more promising solution than the lower
capacity plants, whereas a noticeable increase in the cost of
energy was observed with the biomass increment. Extra
funding was recommended to maintain the financial viability
of the plant in the Spain scenario. Chemical looping
combustion (CLC) technology has potential in this area in
which CO2 removal from the other gas components is not
required. The absence of specific equipment required for CO2
removal makes this process cost- and energy-efficient. This
concept is reported by Richter and Knoche,13 where metal
oxide can be used to support the combustion process rather
than direct contact of fuel with oxygen.
2.2.1. CO2 Remediation through CLC. Zhao et al.14
comprehensively reviewed biomass-based chemical looping
processes and categorized the types of chemical looping
technologies according to the desired output product, for
instance, (a) generation of heat and electricity, (b) generation
of gaseous fuels, and (c) cogeneration of gas and energy. Table
2 shows the general characteristics of the biomass-based
chemical looping in different scenarios with relevant input and
output for both of the designed chambers. A metal is used in
the air reactor or regenerator, which upon heating transforms
into metal oxides to carry the oxygen in the fuel reactor or
combustor. This metal oxide is later reduced due to
consumption of oxygen during biomass combustion and
returns back to the air reactor, and the cycle continues. Figure
3 shows the major factors affecting the CO2 capture efficiency
including char gasification, solid residence time in the fuel
reactor, and CS efficiency in chemical looping combustion.
Adanez-Rubio et al.15 reported the use of a mixture of copper
and manganese oxides in chemical looping combustion (CLC)
with different types of biomass. It was found that oxygen
concentration had a negligible effect on the CO2 capture
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Figure 2. Chemical structure of cellulose, hemicellulose, and structural units found in lignin (SW = soft wood, HW = hard wood. Reprinted from
with permission from ref 151. Copyright 2011 Royal Society of Chemistry.

Table 1. Composition of Different Types of Biomass (Adapted from Refs 143, 10, 144)
composition (%) hard wood soft wood flax hemp sugar cane bamboo pine blue gum
cellulose 40−50 40−50 80 74.1 51.8 54.6 39.9 41.0
hemicellulose 25−35 25−30 13 7.6 27.6 11.4 24.2 19.4
lignin 20−25 25−35 2 2.2 10.7 21.7 27.4 28.1

efficiency. A higher CO2 capture with efficient combustion was
reported. Another recent study by Wang et al.16 showed the
effect of use of different metal ferrites (Cu, Ni, and Co) on the
carbon capture and conversion efficiency. Ni-based ferrite was
found to present lower performance as compared to Cu- and
Co-based ferrites after multiple cycles in a fluidized bed reactor
(Table 3).
Zhang et al.17 reported the use of chemical looping
combustion for partial oxidation of fuel, which can lead to
syngas production. Among the four carriers, CaFe2O4 and
Ca2Fe2O5 were found to be optimal for the production of
partial oxidation of solid fuels. However, the study conducted
C DOI: 10.1021/acs.energyfuels.8b01678
on charcoal may show a limitation with the respected carriers
on employing raw biomass due to different minerals present
according to its source. There are a number of other studies as
well which showed syngas production through chemical
looping gasification technology and showed positive re-
sults.18,19 Luo et al.20 reported the use of iron-based carriers
and found that pure Fe2O3 lacks stability compared to
synthetic Fe2O3/MgAl2O4 and iron ore with a temperature
limit less than 950 °C using methane as a fuel. The detailed
overview of chemical looping combustion technology for solid,
liquid, and gaseous fuels other than the biomass and according
to the different oxygen carriers can be referred to further in
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Nandy et al.21 CLC is also found to be economically

BCLC, BCLG, BCCLP, BCaLC, BCaLG, and SE-BCaLG represent biomass-based chemical looping combustion, biomass-based chemical looping gasification, biomass-based co-production chemical
output

H2
compatible among the CO2 capture technologies for fire
heaters and boilers.22 Oxygen carrier recovery from the ashes
input

H2O
needs to be considered in future biomass studies, and the
lifetime of oxygen carriers with a possible decline in their
gasifier

efficiency on a long-term scale needs to be investigated.

ΔH

<0
2.2.2. Cocombustion with Other Fuels. Co-combustion of
Table 2. General Characteristics of Looping Combustion and Gasification Systemsa (Adapted from Ref 14. Copyright 2017 Royal Society of Chemistry)

biomass and other fuels is also one of the focuses of recent

temp. range,

studies, which brings a variety of outcomes depending on the

600−900

source of the biomass and operating conditions. Gu et al.23

°C

showed that cocombustion of biomass and coal in the presence

of iron ore decreases carbon conversion efficiency with an
increase in temperature due to poor oxygen transport capacity.
O2 + CO2

However, carbon capture efficiency was enhanced with the

temperature increment in the fuel reactor. Luo et al.,24 in
CO2
CO2
O2
O2
O2

another study, reported the cocombustion of coal and biomass

looping process, biomass-based calcium looping combustion, biomass-based calcium looping gasification, and sorption-enhanced BCaLG, respectively.
O2/CO2 carrier

in the presence of a CuO carrier. It was found that biomass

Ni+CaCO3
reduced

MexOy−1
MexOy−1
MexOy−1

helped to raise the efficiency of coal conversion, and it also

CaCO3
CaCO3

increases in the presence of high alkali and alkaline earth

metals in biomass. The potential slagging and fouling needs to
be considered while utilizing biomass in cocombustion
MexOy/heat
MexOy/heat
MexOy/heat

NiO+CaO
CaO/heat
CaO/heat
oxidised

technology. Co-combustion in the presence of additives may

contribute to a decrease in slagging effect.23,24 In another
instant, it was reported that sewage sludge and coal
cocombustion in the presence of a hematite (Fe2O3) oxygen
CO2 rich gas

CO2 rich gas

depleted air
H2 rich gas
H2 rich gas

carrier have the potential to increase the carbonaceous gas

output

syn gas

conversion efficiency and carbon capture efficiency. The

agglomeration also did not occurr, even though coal in this
study contained high alkali and alkaline earth metals due to the
ash,
ash,
ash,
ash,
ash,
ash,

high melting points of the sodium compounds.25 It is possible

to combine woody biomass with sewage sludge to minimize
H2O/CO2
H2O/CO2
H2O/CO2
fuel reactor/combustor

the slagging and fouling potential in the reactor. However,

H2O
H2O

sludge requires a higher temperature and more time in

input

air

reference to the woody biomass for complete combustion

biomass,
biomass,
biomass,
biomass,
biomass,
biomass,

including volatiles and char.

2.3. NOx and SOx Emissions. Even though CO2 emission
is one of the main contributors to environmental pollution and
ΔH
>0
>0
>0
<0
<0

is considered as a benchmark for the so-called green system,

there are, however, other pollutants that are affecting and
temp. range,

600−1000
600−1000
600−1000
600−700
600−700

harming the environment equivalently to CO2. NOx and SOx

°C

emissions are some of the most prominent emission pollutants

emitted during combustion. This highly depends on the
biomass composition, these being one of the main elements
existing in the biomass after carbon, hydrogen, and oxygen.
CO2 rich gas
CO2 rich gas
CO2 rich gas
depleted air
depleted air
depleted air

The NOx emission mechanism is divided into two parts, first

output

through the oxidation of the atmospheric nitrogen during

biomass combustion and second through the oxidation of fuel
containing nitrogen.26
air reactor/regenerator

H2O/CO2/O2
H2O/CO2/O2

2.3.1. NOx and SOx Treatment. These NOx and SOx

input

emissions can be controlled in three ways via precombustion,

during combustion, or postcombustion processes. Although
O2
air
air
air

precombustion primarily emphasizes the selective feedstock for

biomass burning to reduce relevant emissions, the blending of
ΔH
<0
<0
<0
>0
>0

the biomass with other fuels27,28 is, however, also one of the
solutions where not only GHG emissions but also post-
temp range,

600−1200
600−1200
600−1200
850−900
850−900

combustion problems like agglomeration of ash is reduced.

Wang et al.29 reported that the optimum ratio of biomass in a
°C

cofiring scenario is 0.4 to reduce NOx emissions, whereas

further incrementing did not influence the NOx emissions and
combustion efficiency. In another study, it was reported that
SE-BCaLG

biomass-alone burning produced higher NO emissions than

BCCLP

BCaLG
BCaLC
BCLG
BCLC

coal and biomass/coal combustion. This could be due to a

higher nitrogen concentration of the concerned biomass (rice
a

D DOI: 10.1021/acs.energyfuels.8b01678
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Figure 3. Major factors affecting the CO2 capture and oxygen demand in chemical looping combustion. Adapted with permission from ref 140.
Copyright 2017 Elsevier.

Table 3. Carbon Capture and Conversion Efficiencies of Different Metal Ferrites at 850 °C (Adapted with permission from ref
16. Copyright 2017 Elsevier)
carbon conversion (%) carbon capture efficiency (%)
cycle CuFe2O4 NiFe2O4 CoFe2O4 CuFe2O4 NiFe2O4 CoFe2O4
first 95.66 93.53 94.65 95.48 94.04 94.19
second 95.51 91.84 93.78 94.98 92.59 94.07
third 95.46 88.53 93.89 93.65 89.98 93.48
fourth 94.88 86.38 93.21 93.76 87.15 93.40
fifth 94.90 83.85 93.47 93.81 86.30 93.51

husk and wood) and more volatile contents than the coal.
Oxygen staging in the cofiring scenario helped in further
reduction of the NO emissions.30
Combustion technologies are extensively studied to reduce
NOx emissions during the burning process, for instance,
selective noncatalytic reduction,31,32 air staging or two stage
combustion,33,34 and decoupling combustion.35,36 Hongfang et
al.35 reported the use of decoupling combustion for high
nitrogen biomass and encouraged the use of the decoupling
technique above 600 °C. It was also recommended to increase
the burning rate of biomass while maintaining an adequate
char content in the reactor for efficient removal of NOx
emissions. Li et al.37 reported the use of iron oxide as a
catalyst with lignite biomass char to reduce the NO in flue gas
and found that iron oxide increased the removal efficiency.
Temperature also played an important role in this study, where
300 °C showed the highest denitrification. Liu et al.38 and
Khodaei et al.39 reported encouraging outcomes regarding
reductions in the NOx emissions up to 40% through the air
staging technique; however, both of the studies showed an
incremental increase in CO emissions. The complete
combustion was prohibited and particulate emission was
increased in certain cases. Thus, it is recommended to use
the air staging technique coupled with other techniques to
E DOI: 10.1021/acs.energyfuels.8b01678
enhance the reductions of NOx and other GHG emissions.
The oxygen concentration in the combustion chamber also
affects the NOx emission significantly, where the lower excess
oxygen can potentially decrease the NO and N2O emissions.28
2.3.2. Catalytic Remediation. Chen et al.40 presented the
effect of the catalyst on the emission of SO2 and NOx during
the combustion of microalgae and oil shale/microalgae. Oil
shale (10−20%) with microalgae produces the lowest SO2
emissions overall with the time increment at 800 °C. NOx
emissions showed variable behavior in which oil shale addition
decreases the emissions at an early stage, whereas emissions
increase with the time. The MgO catalyst was found to be
helpful in reducing SO2 emissions, and CuCl2 showed the least
effect. In another study, a comparative evaluation of the three
different types of algae biomass (Enteromorpha, Sargassum,
and Chlorella) on SO2 and NOx emissions was reported. SO2
emissions increased with the increase in sulfur content of the
biomass, whereas NOx emissions were not affected by the
nitrogen concentration of biomass. The conversion ratio of the
S and N in relevant biomass algae also showed similar patterns
to those of the emissions.41 On several occasions, emissions of
pollutants from biomass (NOx, PM) are higher than those in
coal-based energy production through combustion,42−44 which
raises serious concerns in this scenario where proper treatment
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Figure 4. Three types of electrostatic precipitators (b) with fluidized boilers (a) classifying the fly ash according to its composition. Reprinted with
permission from ref 152. Copyright 2018 Elsevier.
technologies must be considered prior to utilization of the
biomass for energy generation or heat production.
2.3.3. Post-Combustion Treatment. Post-combustion
techniques involve the treatment of flue gas at the end of
the exhaust system and contribute toward the GHG emission
control. The broad categories in this area are wet and dry
treatment technologies, which serve the purpose of removal of
particulate matter, acidic gases, and heavy metals from the gas.
As the name depicts, dry methods involve the cleaning of gas
through dry technologies, for instance, passing of the flue gas
through filters or an electrically charged medium, which in turn
captures the pollutants. Figure 4 shows three different types of
electrostatic precipitators used for the classification of fly ash
during the biomass burning in fluidized bed boilers. Wet
methods use the universal water solubility principle and
remove the pollutants from the gas through different pieces of
equipment called scrubbers and mop fans etc. A schematic
diagram of the moving bed absorber utilizing copper oxide as a
sorbent for the removal of SO2 and NOx can be seen in Figure
5. Table 4 shows different studies conducted to remove
pollutants from flue gas either during real biomass combustion
or in model flue gas.
2.4. Biomass Ashes. Besides producing greenhouse gases
in the atmosphere, biomass is also responsible for the
F DOI: 10.1021/acs.energyfuels.8b01678
Review
production of ashes in the combustion chamber, which
contains different minerals, trace elements, and heavy metals.
There are two main types of ashes produced during biomass
combustion: (i) fly ash obtained through flue gas cleaning and
(ii) bottom ashes left after the combustion of biomass. The
composition of ashes depends on the biomass uptake of the
respective elements during its lifetime and on its inherent
composition. The ash composition, although, has the potential
to affect the environment; however, a significant problem
occurs in the chamber when reacting the different elements
together producing silicates, sulfates, chlorides, etc.
2.4.1. Slagging and Fouling. The alkalis present in the
biomass react with other minerals and produce intermediate
components. These components react further to create
slagging and fouling in the reactor, which reduces the
productivity of the plant and creates problems in input of
the feedstock, ash congestion, and energy transfer. These
problems also cost economically, where operational costs and
energy are required to remove the ashes and respective
clogging. Figure 6 shows the ash forming elements existing in
various biomass fuels according to its weight. It can be seen
that potassium, silicon, and calcium are the major contributors
in this area. Figure 7 shows the potassium, sulfur, and chlorine
transport during biomass combustion in the form of particles.
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Figure 5. Schematic diagram of moving bed absorber. Reprinted with permission from ref 141. Copyright 2013 Elsevier.

Table 4. Pollutants Removal from Gas through Different Post-Combustion Technologies

technology type of gas efficiency combustion chamber feedstock pollutant refs
electrostatic precipitator flue gas and ∼ 98% for flue gas and ∼75% boiler (50 kW) and gasifier wood pellets particulate 145
biogas for biogas (100 kW) matter
wet scrubber system with chlorine flue gas >97% for SO2 removal and artificial flue gas NOx 146
dioxide >80% for NOx produced SO2
condenser flue gas ∼ 57% for PM2.5 and 43% for industrial boiler coal fine particles 147
PM10
spray scrubber with 30% mono- flue gas ∼90% CO2 removal pilot plant CASPAR artificial flue gas CO2 148
ethanolamine produced
moving bed absorber with copper flue gas ∼85% fly ash life cycle test system coal SO2 141
oxide sorbent ∼90 SO2 and NOx removal NOx

KCl and K2SO4 can be found in the form of coarse particles
known as PM10 and in the form of aerosols. In a detailed study
presented by Bogush et al.,45 different types of biomass ashes
generated throughout the UK were reported with the goal of
comprehensive characterization. Most of the ashes produced
from the combustion of meat, poultry litter, and bone meal
tend to be alkaline with a high concentration of P
(phosphorus), K (potassium), and Ca (calcium). The high
concentration of P and K allows the use of this end-product in
agricultural fields. Vassilev et al.46 presented a comprehensive
review on ash element presence in different types of biomass
G DOI: 10.1021/acs.energyfuels.8b01678
(532 varieties) and classified the biomass accordingly (Figure
8).
2.4.2. Factors Affecting the Slagging and Fouling. There
are many factors which influence the creation of slagging and
fouling through biomass combustion, including peak temper-
ature, heating rate, biomass feedrate, etc. However, calculating
the effect of biomass slagging potential is understood by the
relations developed for coal combustion. These relations are
generally not suitable for accurate prediction. Garcia-Maraver
et al.47 presented a comprehensive study to evaluate the
established relationships and indices to calculate the biomass
slagging capacity, and there was no direct relationship found
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Figure 6. Elements contributing toward ash production in biomass during combustion (db = dry basis). Reprinted with permission from ref 153.
Copyright 2017 Elsevier.

Figure 7. Transport pathway of potassium, chlorine, and sulfur from biomass to fine particles during combustion of biomass. Reprinted with
permission from ref 142. Copyright 2017 Elsevier.

among the current indices for biomass fuels. Hence, it was
recommended to obtain real time data for biomass combustion
scenarios and revaluate the effect of these indices and establish
relationships as per the diversity of their composition and
combustion behavior.
Weber et al.48 reported the high temperature (950−1200
°C) effect on ash deposition to minimize the effect of alkali
salts on ash condensation. Ash deposition and sticking
efficiency increased at 1170 °C (1.2−2.4%; 0.4) as compared
to 970 °C (0.2−0.5%; 0.03−0.09), respectively. This also
agrees with the results presented by Yang et al.,49 in which an
increase in sticking efficiency was observed with the increase in
furnace temperature. The deposition time also plays an
important role that increases the deposition due to a
thermophoresis phenomenon and local temperature variation.
H DOI: 10.1021/acs.energyfuels.8b01678
Kleinhans et al.50 explained the deposition of ash according to
its size and contents. Particle viscosity and kinetic energy are
the main parameters explaining the sticking behavior of ash
particles. Alumino-silicate particles having a small size stick
together due to low kinetic energy, whereas large particles rich
in iron are mainly effected by low viscosity values. At another
instant, fluidized temperature was shown as a critical factor due
to silicate melt induced slagging. The higher fluidized
temperature reduces the high-temperature silicate-melt-
induced slagging.51 In a separate study, Niu et al.52 presented
an alkali based slagging mechanism in boilers (Figure 9).
Slagging was defined by the chlorine and sulfur ratios (Cl +
K2O + Na2O/SiO2 + Al2O3 and Svolatile + K2O + Na2O/SiO2 +
Al2O3, respectively). Slagging was predominant with chlorine
and sulfur ratios higher than 2.4 and 1.9, respectively.
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Figure 8. Classification of ash produced from biomass combustion according to its chemical composition. Reprinted with permission from ref 46.
Copyright 2017 Elsevier.
Increasing chlorine and sulfur ratios expands the growth of
potassium chloride (KCl) and aphthitalite, which ultimately
causes the intensification of the slagging process.
2.4.3. Biomass Ash Applications. As ash production is
inevitable during biomass combustion as a byproduct, it has
found its way into many applications, for instance, as a binder
replacement in cementitious composites,53 in biogas purifica-
tion by the removal of hydrogen sulphide,54 and in sewage
sludge treatment.55 Recently, Ribeiro et al.56 reported the use
of industrial fly ash and domestic ash use for soil fertility and
plant growth. Domestic ash was found to be effective in the
transferring of macronutrients such as K, P, and Ca to the soil.
However, an increase in plant growth was not observed. Cruz-
Paredes et al.57 compared phosphorus fertilizer application
with that of biomass ashes in a barley crop and pointed out
that biomass ashes were not a significant factor in altering the
yield of the crop. Hence, they can be used as a substitute for
phosphorus fertilizer. A long-term study in this scenario is
recommended to determine the cyclic effect of ashes on overall
production behavior. In another study by Zhang et al.,58 the
replacement of potassium fertilizer with ash tablets (6 mm × 2
mm to 15 mm × 5 mm) was studied for the slow availability of
nutrients to the plants. The reported methodology reduced the
potassium release rate as compared to powder ash to 1/60th;
however, it is still greater than conventional potassium
fertilizer. The bigger sized tablets (210 mm × 70 mm) and
smaller diffusion coefficient are recommended in the use of
biomass ash as a fertilizer.
3. PYROLYSIS
Thermochemical processing addresses the key challenges faced
by a combustion system as mentioned in the previous section.
This processing technique reduces CO2 emissions, properly
utilizes the biomass, and diverts the end-products’ yield
according to the desired outcome. There are three subgroups
in this processing technique: (i) torrefaction, (ii) pyrolysis, and
I DOI: 10.1021/acs.energyfuels.8b01678
Review
(iii) gasification. There is a new emerging area in this scenario,
hydrothermal processing, which also contains three subcate-
gories: (a) hydrothermal carbonization, (b) hydrothermal
liquefaction, and (c) hydrothermal gasification. All of the
processing of biomass in this category involves controlled
heating in a limited or oxygen-free environment where biomass
is primarily converted into three components: (i) gas, (ii)
liquid, and (iii) solid. Table 5 shows a typical distribution of
these products through each of the processes. The controlled
conditions, type of fuels, and their product’s use are discussed
in detail in the subsequent section.
Pyrolysis is a process of heating the organic materials in the
absence or limited supply of oxygen at an elevated temperature
(<700 °C).59 It contains mainly three subcategories: (a) slow
pyrolysis, (b) intermediate pyrolysis, and (c) fast pyrolysis.
Intermediate pyrolysis contains features of both slow and fast
pyrolysis in which the major product is liquid (50%) and the
rest is solid (25%) and gas (25%).60 Cellulose, hemicellulose,
and lignin convert to tar, noncondensable vapor, and char
during pyrolysis at 150−350 °C, 275−350 °C, and 250−500
°C respectively.
3.1. Slow Pyrolysis. Slow pyrolysis is the heating of the
biomass/organic material in the absence or with a limited
supply of oxygen with a slow heating rate and predominantly
produces a solid product called biochar or simply char. This
obtained char product contains different properties according
to the type of feedstock and can be used for different
applications. Most of the organic waste derived from different
sources including but not limited to wood waste,61 farm and
agricultural waste,62 municipal solid waste (MSW),63 and
industrial waste64 can be utilized to process the waste and
produce char for further use in different applications. Char
produced from lignocellulosic biomass and agro-industrial
waste is found to be more suitable for solid fuel production65
due to retention in energy density; however, poultry litter char
is suitable for soil amendment. Zhang et al.66 have done a
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soil fertility, whereas sugar cane char can be a source of

potassium and phosphorus.

Figure 10. Categorization of biochar according to the feedstock type.

Reprinted with permission from ref 66. Copyright 2017 Elsevier.

The other significant factor affecting the char yield and

properties is the reaction conditions in the reactor. For
instance, increasing peak temperature and increasing residence
time lead to less yield and modify the properties according to
the char produced at relatively lesser peak temperatures. The
peak temperature is the temperature at which the pyrolysis
reaction terminates and products starts to cool down. Overall,
a higher temperature leads to a higher carbon content,
thermally stable char,67 greater micropore volume, and higher
surface area.68 The increasing temperature of the pyrolysis also
reduces the nutrients utilized by plants, for instance,
phosphorus (P), potassium (K), and nitrogen (N);65 hence,
it is not recommended for improving soil fertility. The
residence time of the feedstock in the reactor also contributed
to a change in properties; however, a significant effect on
residence time was observed in low temperature (350 °C)
Figure 9. Slagging mechanism due to alkali during combustion of pyrolysis rather than relatively high temperature (>600 °C)
biomass. Reprinted with permission from ref 52. Copyright 2014
Elsevier.
pyrolysis.
3.1.1. Activation and Applications of Char. Char proper-
Table 5. Approximate Yields of the Products Obtained by ties can be changed post-pyrolysis through different techniques
Thermochemical Conversion of Biomass (Adapted with called physical and chemical activation. This process removes
permission from ref 149. Copyright 2014 Elsevier) the volatiles and improves the surface area, which is valuable in
various applications. In a recent study by Bardestani and
product distribution (wt %) Kaliaguine,69 steam activation and mild air oxidation were
technology solid (char) liquid (bio-oil) gas compared, and it was found that surface area increased 20
slow pyrolysis 35 30 35
times through the steam activation process. However,
fast pyrolysis 10 70 20
functional groups decreased. Mild air oxidation on the other
gasification 10 5 85
hand, increased the functional groups from 44 to 104.6 μmol
m−2. Genuino et al.70 also reported an increase in surface area
(+64%) and adsorptive properties after thermal and chemical
comprehensive study on char production from four different activation of MSW derived char. More than 99% dye removal
types of biomass (pine, peanut shell, sugar cane, and oak) and was achieved with activated char in the presence of a
categorized the char into three categories depending on the concentration up to 25 mg L−1. Wang et al.71 reported the
elemental composition (Figure 10). Char produced from increase in adsorption properties for acid red 18 dye with the
peanut shell contains several elements suitable for plants and use of nitrogen doped activated carbon prepared through
J DOI: 10.1021/acs.energyfuels.8b01678
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Figure 11. Bio-Oil Upgrading Process in a Nutshell. Adapted with permission from ref 150. Copyright 2011 Elsevier.

Table 6. Catalytic Upgrading of the Bio-Oil through Zeolite Cracking (Adapted with permission from ref 150. Copyright 2011
Elsevier)
catalyst setup feed time (h) pressure (bar) temperature (°C) oil yield (wt %)
GaHZSM-5 continuous bio-oil 0.32 1 380 18
H-mordenite continuous bio-oil 0.56 1 330 17
H−Y continuous bio-oil 0.28 1 330 28
HZSM-5 continuous bio-oil 0.32 1 380 24
HZSM-5 continuous bio-oil 0.91 1 500 12
MgAPO-36 continuous bio-oil 0.28 1 370 16
SAPO-11 continuous bio-oil 0.28 1 370 20
SAPO-5 continuous bio-oil 0.28 1 370 22
ZnHZSM-5 continuous bio-oil 0.32 1 380 19

ammonium chloride and ammonium acetate in the presence of
microwaves.
Char use in heavy metals removal has been reported on
several occasions72−74 and found to have a significant effect on
adsorption properties after activation. Ahmad et al.75 recently
reported the effect of potassium rich char on the removal of
heavy metals (Cu, Cd, and Pb) in aqueous solution avoiding a
separate activation. Banana peels and cauliflower leaves were
used to produce the biochar. Banana peel char was found to
enhance the sorption capacity more than cauliflower char due
to electrostatic attraction being the main driver in sorption
capacity. In another instant, rice straw char produced at 600 °C
was investigated for the adsorption of Cu and Zn in a single
and binary metal system. Biochar was highly active in
adsorbing the respective metal in the beginning; however,
after 4 h, it reaches equilibrium. Char was found to be highly
sorbent in the presence of a single metal and reduces the
efficiency in the presence of both metals. Adsorption of Zn was
affected the most in a binary metal system.76
Char from different materials is also observed to be an
effective sorbent of NH4.77 Char use in other applications is
K DOI: 10.1021/acs.energyfuels.8b01678
being recognized for heavy metal removal and soil improve-
ment and amendment. For instance, char use in wood
polypropylene composites is comprehensively reported by
Das et al.,78,79 and positive results were obtained for
mechanical and fire resistance properties. Similarly, char use
in concrete applications improved the strength of concrete.80,81
It is expected that with the passage of time, char use in
different applications will further add value and will continue
to increase its potential with several varying properties.
Although char is a highly stable carbon material with years
of carbon storage potential, nonetheless, the use of char as a
fuel is limited, and an alternative technology of receiving
liquid-based fuel products in the pyrolysis category is fast
pyrolysis.
3.2. Fast Pyrolysis. Fast pyrolysis yields a high amount of
liquid product called bio-oil at high heating rates, which
sometimes range from a few milliseconds to seconds. The
obtained resultant product thus contains several properties and
has the potential to be used in several fuel- and chemical-based
applications. The significant parameter in this scenario is
heating rate, which determines the total product output and
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Figure 12. Bio-oil and kitchen waste oil upgradation pathway over HZSM-5 catalyst. Reprinted with permission from ref 86. Copyright 2018
Elsevier.
properties. Bio-oil produced through this process contains
many challenges including high viscosity, low heating value,
and water fractions. There are two routes considered after the
production of bio-oil: either convert it into biofuel through
upgrading (cracking82 mechanism, steam reforming,83 and
hydrodeoxygenation84) or convert it into suitable chemicals
which can further be processed to use in different applications.
Figure 11 shows the different process methods generally used
to upgrade bio-oil into useful products.
3.2.1. Bio-Oil Upgradation. 3.2.1.1. Catalytic Cracking.
Hew et al.85 have done catalytic cracking of bio-oil produced
from empty fruit bunch and reported 400 °C, 15 min, and 30 g
of catalyst as optimum parameters for conversion of bio-oil to
gasoline. The conversion rate was remarkably more than 90%.
Table 6 shows a different zeolite cracking catalyst utilization
for upgrading of the bio-oil and its yield potential. As can be
seen, the yield is less than 30% in all cases. Combined catalytic
cracking is one of the recent interests of today’s research in
which bio-oil is combined with different hydrocarbon-rich
materials to produce more effective products. For instance,
recently, Ma et al.86 reported the upgrading of a mixture of bio-
oil and kitchen waste oil with the use of catalyst HZSM-5.
Kitchen waste oil acted as a hydrogen supplier, which helped in
the formation of hydrocarbons from unsaturated oxygenated
compounds. Figure 12 shows the conversion chain of different
reactions occurring during the combined upgrading of kitchen
waste oil and bio-oil produced from saw dust at 550 °C. In
another study, bio-oil was mixed with ethanol, and cocracking
L DOI: 10.1021/acs.energyfuels.8b01678
Review
was performed over the Ni-ZSM-5/MCM-41 catalyst. A
significant drop in acid content (0.1 wt %) was achieved and
converted acids to ketones.87
3.2.1.2. Catalytic Steam Reforming. Catalytic steam
reforming helps to produce useful gaseous products (H2,
CO, etc.) from bio-oil or pyrolysis oil and helps in elimination
of carbon-rich phases. There are number of studies done on
the steam reforming process and optimization of hydrogen
yield.88,89 Nabgan et al.90 presented a comprehensive review
article recently on the subject matter. Quan et al.91 conducted
the steam reforming of bio-oil through an Fe/olivine catalyst,
which helped in conversion of the phenolic-rich oil into light
gas phases such as CO, H2, and CH4. The optimum conditions
reported are 800 °C with a weight hourly space velocity of 0.5
and a steam to carbon ratio of 2 to achieve a carbon conversion
efficiency of 97%.
Bimbela et al.92 obtained the highest H2 production with Ce
impregnation onto a conventional Ni−Mg−Al catalyst. Ce
impregnation at 0.5% produced the highest yield of H2 as
compared to the Ni/Mg−Al catalyst and provided stable H2
production. In another instance, approximately 80% hydrogen
production was achieved, and 97% carbon conversion was
attained at 850 °C and a steam to carbon ratio of 5:1. Most of
the carbon removal can be achieved through combustion in an
air flow at 600 °C.93 Char is found to be an effective catalyst in
the steam reforming process, and a sufficiently high yield of
hydrogen of approximately 89% was obtained at 900 °C, a
steam to bio-oil model compound ratio of 3, and a weight
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hourly space velocity equal to 1. This high efficiency was respectively.100 Hemicellulose degradation causes the produc-
obtained due to alkali and alkaline earth metals present in char, tion of CO2, formic acid, and tar. The other products obtained
which influenced the water adsorption and facilitated the during degradation are xylose, acetol, CO, and 2-furalde-
formation of reactive hydroxyl groups.94 hyde.101 Gaseous product yields obtained during hemicelluose
3.2.1.3. Catalytic Hydrodeoxygenation. Bio-oil tends to pyrolysis are given in Table 7. It can be seen that CO2 is found
contain a high amount of oxygen, which results in less energy
yield as compared to conventional fuels. Hydrodeoxygenation Table 7. Gaseous Products Produced during the Fast
is the process of oxygen removal in bio-oil and produces Pyrolysis of Hemi-Cellulose (Adapted with Permission from
energy-rich products which can be called biofuel. This product Ref 102. Copyright 2010 Elsevier)
has the potential to be incorporated with conventional fuels.
compounds (wt
Although significant advances have been reported recently, %) 425 °C 475 °C 510 °C 570 °C 625 °C 690 °C
nevertheless, further research is required to further improve the
CO2 25.01 24.54 25.61 25.78 24.79 22.87
quality of biofuels. Cheng at al.95 have done in situ
CO 5.35 5.23 6.02 6.93 9.24 13.33
hydrodeoxygenation of pine sawdust bio-oil over a Pd/C
H2 1.08 1.60 2.35 2.49 3.29 3.34
catalyst. This is a relatively new technique in which hydrogen is
acetic acid 4.44 4.40 3.82 3.20 2.45
not provided through an external source, despite the water 1,4-anhydro-D- 3.84 3.43 2.85 2.01 0.69
present in the bio-oil being used to produce hydrogen. The xylopyranose
optimum temperature was reported to be 250 °C, yielding a furfural 1.94 2.30 2.40 2.86 3.16
heating value of oil of 30 MJ/kg with a high hydrocarbon methanol 0.81 1.01 1.11 1.13 1.14
content of 24%. acetone 0.69 0.77 0.84 1.00 1.06
This technique was earlier reported by Cheng et al.,96 in
which zinc hydrolysis was used despite an external hydrogen
supply. However, a higher treatment temperature (<400 °C) to be the highest production gas followed by CO and H2, and
was selected, and increasing the temperature resulted in among the organic compounds, acetic acid was produced at the
improved hydrocarbon content (38−69%) and heating values highest concentration followed by 1,4-anhydro-D-xylopyranose
(33 MJ/kg). Similarly, Mosallanejad et al.97 presented another and furfural. Acetic acid and 1,4-anhydro-D-xylopyranose were
approach of in situ upgrading of bio-oil through hydro- reduced with the increase of temperature, and furfural
deoxygenation with the use of a pulsed corona discharge concentration increased with the increase of peak temper-
(plasma reactor). The hydrogen was produced through methyl ature.102 Hemicellulose degradation into bio-oil, gas, and char
decomposition rather than the separate addition of hydrogen. is shown in Figure 13.
This study was done on model compound 4-methylanisole Cellulose exists anywhere between 40 and 90%, depending
rather than bio-oil derived from biomass; hence further on the type of the biomass. Cellulose pyrolysis is divided into
detailed study is required on original bio-oil as well as an three phases, development of active cellulose or anhydrocellu-
evaluation of the detailed effect on hydrogen production. lose, depolymerization, and the char production process. The
3.2.1.4. Catalytic Hydrocracking. Hydrocracking is the phenomenon of active cellulose occurs before 300 °C due to
process of converting hydrocarbons containing a high boiling dehydration, depolymerization between 300 and 390 °C, and
temperature to low boiling temperature hydrocarbons. This char production effected from 380 up until 800 °C.
also includes the use of a catalyst during the reaction which can Depolymerization is the step which causes the highest
help to reduce the bio-oil into simpler compounds. A study by production of volatile compounds.103 Figure 14 showed the
Lee et al.98 was reported for selective hydrocracking done on degradation of cellulose to different volatile compounds
the tetralin model compound in the presence of different obtained during fast pyrolysis. There are several types of
catalysts (Ni/H beta catalyst with Ni contents from 1 to 10%, linkages existing in lignin between carbon and carbon, ether,
Ni−Sn/H beta, and CoMo-S/H beta) to record the benzene, and ester, for instance, β-O-4, β-β, β-5, 4-O-5, α-O-4, 5−5, etc.
toluene, and xylene production. The yield order is as follows Figure 15 shows a β-O-4 type linkage model compound during
Ni−Sn/H beta > CoMo-S/H beta > Ni/H beta. In another the pyrolysis and degradation into subcompounds upon
recent study, Upare et al.99 showed that a synthesized catalyst thermal treatment. Lignin pyrolysis divides into two temper-
(cobalt promoted Mo/β with different metallic loadings (0.5− ature categories. Initially, alkyl chain conversion and breaking
1.5)) promoted hydrocracking of the model compound tetralin of some of the linkages occurs up to 400 °C, and later type H
and bio-oil. The highest yield of benzene, toluene, and xylene phenol concentration increased in bio-oil, and type S phenol
was produced from the Co/Moβ catalyst at 0.5 impregnation concentration decreased with the increase in temperature up to
in both cases; however, the studied compounds were produced 800 °C.103 As compared to cellulose and hemicellulose where
in less yield in bio-oil (55%) than in the model compound gas, tar, and char are the main products of the pyrolysis, lignin
tetralin (63%). This also shows a possible variation in the produces gas, char, phenols, and lignin derivatives, which can
results while conducting the experiments with bio-oil rather later be distilled into different fractions.104 Figure 16 presents
than model compounds. the lignin conversion into chemicals during fast pyrolysis from
3.2.2. Cellulose, Hemicellulose, and Lignin Degradation 400 to 700 °C in a simple equation form.
during Pyrolysis. Cellulose, hemicellulose, and lignin, the basic
constituent of the biomass, are responsible for the complex 4. GASIFICATION
chemical reactions upon heating and converting into mixed Gasification treatment of the biomass is well studied and
crude oil during fast pyrolysis. These three components can be implemented commercially as compared to pyrolysis due to
identified according to their degradation pattern in the the obtained product being easily accessible and requiring less
pyrolysis. Hemicellulose, cellulose, and lignin degradation post-recovery work. The major product is syngas, which can be
occur at 220−315 °C, 315−400 °C, and >400 °C, used in electricity generators or in boilers to produce energy
M DOI: 10.1021/acs.energyfuels.8b01678
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Energy & Fuels
Figure 13. Hemicellulose degradation under pyrolysis into bio-oil, gas, and char. Reprinted with permission from ref 154. Copyright 2015
American Chemical Society.
and used as a chemical feedstock. The gasification process
consists of four main stages: (i) oxidation, (ii) drying, (iii)
pyrolysis, and (iv) reduction.105 From drying of the biomass
through pyrolysis, oxidation, and reduction of tar, biomass goes
through several physical and chemical changes, which lead to
producing CO, CO2, H2, and other gases. These products were
further processed, leading to the production of different types
of fuel, including methanol, Fischer−Tropsch processing to
produce biofuels, pure hydrogen production as a fuel, methane
production, etc. These products not only contribute to
renewable fuels but also help to cope with other fossil-fuel-
related use in chemical production. Different types of gasifiers
are used in the gasification process from conventional updraft
or downdraft gasifiers to modern gasifiers like plasma. Figure
17 shows a schematic diagram of different types of gasifiers
with their advantages and disadvantages.
Gasification like other processing techniques is also
influenced by the reaction conditions, including peak temper-
ature, residence time, and heating rate. Similarly, the
atmosphere inside the reaction chamber also affects the
resultant properties of syngas and char. Tang et al.106 reported
the effect of a N2 and CO2 inert atmosphere on char properties
from MSW and found that surface area and porosity are
significantly affected by a change in atmosphere. CO 2
improved the properties of the char as compared to N2 up
tp 700 °C; however, porosity in the CO2 atmosphere degraded
due to gasification. Another study by Tang et al.107 showed
that CO2 acts as an inert atmosphere under 600 °C, whereas it
shifts to a reaction atmosphere above 600 °C, which leads to
the higher production of syngas, facilitating the gasification
N DOI: 10.1021/acs.energyfuels.8b01678
Review
process. Mainly CO2 is being employed to improve the char
properties and enhance the gasification process rather than
using it as an inert gas for biomass. Recently, Azuara et al.108
reported that CO2 atmosphere instead of N2 reduced the CO2
emission; however, CO production increased comparatively.
4.1. Advances in Syngas Treatment. Syngas, which is
the combination of H2 and CO2, requires cleaning due to
different pollutants (sulfur, nitrogen, tars, particulate matter,
etc.) exists depending on the type of feedstock and operating
conditions. The permissible limits for the pollutants in syngas
with respect to the application are given in Table 8. Woolcock
et al.109 presented a comprehensive article on the syngas
cleaning technologies and divided the technologies into three
categories: hot gas cleaning (>300 °C), warm gas cleaning, and
cold gas cleaning (≤100 °C). Shi et al.110 proposed a new
methodology through simulations to remove organic con-
taminants from syngas by introducing oxygen on the principle
of thermodynamic equilibrium. The resultant syngas contains a
high amount of the desired product (H 2 + CO 2 ),
approximately 72% in the preheating category. Preheating
decreased the oxygen, fuel, and steam consumption. However,
a real biomass-based syngas needs to be tested for thorough
evaluation of the proposed work. Recently, Chen et al.111
developed an improved device (moving granular bed filter) to
remove particulate matter from the syngas in a cold test and
found it to remove the particulate matter up to 87% for particle
sizes ranging from 0.1 to 0.5 μm with an inlet dust
concentration of 15 000 ppmw. A schematic diagram of the
filter is shown in Figure 18. However, the filter is less effective
for particle sizes greater than 0.5 μm.
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Figure 14. Pyrolysis of cellulose to volatiles. Four possible pathways from glycosidic cleavage to the formation of (1) formic acid, CO2, and 2,5
dihydroxy-3-pentanal; (2) formaldehyde and 2,3-hydroxy-4-pentanal; (3) glyoxal and 3-(vinyloxy)-2-oxiranol; (4) formaldehyde, carbon monoxide,
and 4-hydroxy-2-butenal; (5) malondialdehyde and a radical intermediate. Adapted with permission from ref 155. Copyright 2012 Royal Society of
Chemistry.

Filippis et al.112 successfully reduced the tar and particulate
matter (PM) in syngas through the addition of a second fixed
bed reactor containing Al2O3 spheres. The secondary reactor
reduced the tar and PM approximately 60% and 84%,
respectively. After wet scrubbing, the tar and PM were reduced
to a great extent, containing less than 12 and 7%, respectively.
On the other hand, Diego et al.113 reported a high tar removal
efficiency through catalytic filter candles in a dual fluidized bed
gasifier for biomass gasification. The tar conversion was
reported up to 80% with tar removal efficiency up to 95% at
850 °C in the filter enclosing catalytic layer integrated with an
activated alumina foam tube.
Akay et al.114 reported that sulfonated polyHIPE polymers
(s-PHP) positively influenced the tar removal from the syngas
O DOI: 10.1021/acs.energyfuels.8b01678
in the range of 80−95%, and dew point depression reduced
from 90 to 70 °C. The authors encouraged the use of tar
loaded s-PHP into soil to enhance the crop productivity. In
another recent study, lime was also found to be effective in
reducing tar concentration during gasification. Tar yield was
found to be decreased approximately 8 times relative to the
nonlime (silica sand) study in a fluidized bed reactor. Tar dew
point was also noted to be decreased to 71 °C from 124 °C.115
Peng et al.116 reported that cogasification of coal/biomass
helps improve the tar removal in the presence of carbonates
(K2CO3, KHCO3, and NaHCO3) as catalysts with pure oxygen
and steam. The highest yield is obtained through the K2CO3
catalyst.
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Figure 15. Pyrolysis mechanism explained for β-O-4 type lignin model compound. Reprinted with permission from ref 156. Copyright 2013 Royal
Society of Chemistry.

Figure 16. Catalytic and noncatalytic process for lignin conversion during fast pyrolysis. Reprinted with permission from ref 157. Copyright 2012
Elsevier.

Plasma has gained considerable attention recently toward H2 and CO concentrations were achieved with a low amount
syngas treatment to remove impurities. Hrabovsky et al.117 of impurities produced. The composition of the gas recorded
treated syngas produced from different feedstocks (wood was similar to that predicted by the thermodynamic
pellets, crashed waste polyethylene, fine sawdust, and equilibrium calculations. Wnukowski et al.118 recently also
pulverized lignite) with steam plasma at a very low flow rate observed an increase in H2 and CO concentration upon
(18 g/min) for a 1 kg/min flow rate of treated material. High treatment with microwave plasma, considering benzene as a tar
P DOI: 10.1021/acs.energyfuels.8b01678
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Figure 17. Biomass gasifiers traditionally used with their pros and cons. Adapted with permission from ref 158. Copyright 2018 Elsevier.

model compound; however, the mechanism described by the The authors also suggested the use of oxygen as a gasifying
authors suggested that methane presence reduced the agent to improve the H2 concentration in gas and reduce the
conversion efficiency up to 60% due to reforming of benzene. nitrogen. In another study, a hybrid plasma and catalytic
Q DOI: 10.1021/acs.energyfuels.8b01678
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Table 8. Permissible Limits for the Pollutants in Syngas Jia et al.,122 on the other hand, presented a pathway to improve
According to the Applications (Adapted with Permission the quality of syngas produced from woodchip gasification.
from Ref 109 from Elsevier) Char was impregnated with potassium salts (KCl, KOH,
K2CO3, and CH3COOK); however, maximum hydrogen yield
applications
(197.2 g/kg) was obtained with a 6 wt % KOH solution. High
methanol FT temperature increased the syngas production, whereas it led to
contaminant IC engine gas turbine synthesis synthesis
lowering the hydrogen yield. Oxygen helped to convert the
nitrogen (NH3, <50 μL/L <0.1 <0.02 char and adjust the H2/CO ratio to enhance the quality of
HCN) mg/m3 μL/L
alkali <0.024 <0.01
syngas.
μL/L μL/L Gupta et al.123 developed hybrid solar−thermal power
inhibitory <0.01 generation with the use of syngas combustion as an alternating
compounds μL/L heat source. The system contained a maximum fuel thermal
class 2-heter atoms, <1 μL/L input of 34 kW and a turn down ratio of 1.67. The optimum
BTX
reported equivalence ratios were 4 and 5 with a quick start-up,
tars (condensable) <100 mg/m3 <0.1
mg/m3 stable operation, and low heat loss of approximately 20−27%.
particulate (soot, <50 mg/m3 <30 mg/m3 <0.02 Rajbongshi et al.124 presented a PV−biomass−diesel hybrid
dust, char, ash) (PM10) (PM5) mg/m3 energy system for rural electrification, and cost analysis was
sulfur (H2S, COS) <20 μL/L <1 mg/m3 <0.01 done for a 19 kW peak load with a demand of 178 kWh/day.
μL/L The cost was found to be U.S. $0.145/kWh for an off grid
halides (primarily 1 μL/L <0.1 <0.01 system; however, the energy price reduced to U.S. $0.064/
HCl) mg/m3 μL/L
kWh. Kohsri et al.125 recently proposed a hybrid syngas/PV
system for a continuous supply of electricity using a battery
powered system. The specific fuel consumption of syngas was
found to be at 3.14 N m3/kWh with an efficiency of the bio-
power system around 16.9% and the overall efficiency at
34.3%. The operating plant contained 12.28 kW solar panels,
33.7 kW of syngas genset, 13.8 kW of bidirectional converter,
and 60.9 kWh of battery capacity.
Zhao et al.126 synthesized a novel catalyst from Cu−Mn
mixed oxides through calcination and cocatalyst CaO-ZrO2 to
convert syngas into methyl formate. Methyl formate was
formed due to a nucleophilic addition−elimination reaction
mechanism and carbonylation of methanol and CO. Liquid
petroleum gas (LPG) synthesis was achieved from syngas by
synthesizing the CZ@H-β-P catalyst by preparing the zeolite
through a hydrothermal technique and later coated on a Cu/
ZnO core with Ludox.127 Moreover, the catalyst promoted the
Figure 18. Moving granular bed filter for syngas cleaning. Reprinted
intermediate reactions like conversion of methanol through
with permission from ref 111. Copyright 2018 Elsevier. dehydrogenation to dimethyl ether, which participated in the
generation of LPG. CO conversion and hydrocarbon selectivity
were recorded at 61.8% and 64.2%, respectively.
conversion of toluene as a model tar compound was tested by Syngas combustion was improved in internal combustion
Liu et al.,119 who found that the catalytic effect increased the engines through methane enrichment, which resulted in quick
conversion efficiency with plasma. The highest conversion and smooth combustion behavior relative to syngas and
efficiency recorded was 52% in the presence of 20 wt % Ni/ compressed natural gas alone.128 This also improved the brake
Al2O3 catalyst in a dielectric barrier discharge plasma reactor. thermal efficiency (30.2%) and brake specific fuel consumption
The mechanism of toluene conversion as a model tar (21.3%) and reduced the CO emissions. Indrawan et al.,129
compound during gasification can be seen in Figure 19. reported the use of syngas in a spark ignition engine with a
Furthermore, chemical looping is also finding its way in the capacity of 10 kW after modification to observe the parameters
treatment of biofuels besides combustion. More et al.120 like air to fuel ratio and feeding the syngas directly from the
presented a new approach to catalytically convert the methane reactor. A total of 5 kW power was produced with a specific
in syngas to produce H2 gas. Methane was cracked over a Ni fuel consumption of 1.9 kg/kWh and net electrical efficiency of
catalyst (carbon carrier), which is later regenerated by 21.3%. CO, CO2, SO2, and NOx emissions were produced at a
oxidizing the carbon via CO2, hence reducing the chances lower concentration than that using the natural gas based
for CO production. engine. However, the fuel consumption was higher, and
4.2. Advances in Syngas Applications. Zhang et al.121 produced output was lower than that of the natural gas burning
recently presented the influence on combustion properties engine. Syngas and biogas cocombustion in internal
(adiabatic flame temperature, laminar flame speed) with the combustion engines was studied by Kan et al.130 to understand
variation in syngas composition. Adiabatic flame temperature the combined behavior. The syngas fueled engine performed
was found to be less affected by the variation in syngas; better than the biogas fueled one, and hydrogen concentration
however, flame speed is significantly affected by fuel variation. positively affected the indicated thermal efficiency of syngas
Hydrogen variation at lean combustion affects the flame speed utilization in IC engines. However, it reverses when ignition
approximately 80%; however, methane had a negligible effect. advance is relatively higher. The combined combustion of both
R DOI: 10.1021/acs.energyfuels.8b01678
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Review

Figure 19. Gasification mechanism of toluene as a model tar compound in dielectric barrier discharge plasma reactor (a) energetic electrons and
excited Ar (b) OH radicals. Reprinted with permission from ref 119. Copyright 2017 Elsevier).

gases led to a reduction of knocking and NOx emissions. Al-

attab et al.131 proposed a new technique to remove the step for
external compression of syngas by injecting the air−syngas
mixture directly in the micro-gas-turbine’s compressor. This
proposed technique was tested by developing a pressurized
cyclone combustor with a micro-gas turbine. Stable syngas
combustion was achieved for an air−fuel ratio of 3.3−4.1, and
NOx and CO emissions were noted below 250 and 15 ppm,
respectively. The total energy pathway of the studied system is
shown in Figure 20.
Additionally, Pardo-Planas et al.,132 simulated the hybrid
gasification and fermentation process for ethanol production
from syngas. The potential of 36.5 million gallons of anhydrous
ethanol production was observed through the utilization of
1200 tons of switchgrass. Syngas fermentation can yield
approximately 97 gallons of ethanol per dry ton of biomass.
Schematic diagram of the process is shown in Figure 21.
Recently, Sun et al.133 produced ethanol from the syngas with
the help of char fermentation media from four different sources
(switchgrass, forage sorghum, red cedar, and poultry litter).
Red cedar and poultry litter derived char enhanced ethanol
production significantly up to 16% and 59%, respectively,
relative to a yeast extract medium. This was due to the
inorganic elements present in char, which were released during
fermentation and reduced the acid stress on anaerobic bacteria,
leading to the enhanced ethanol production. Figure 20. Energy distribution during the syngas production in a
4.3. Supercritical Water Gasification (SWG). Super- microgas turbine. Adapted with permission from ref 131. Copyright
critical water gasification is also a biomass conversion 2018 Elsevier.

i xy
CHxOy + (2 − y)H 2O → CO2 + jjj2 − y + zzzH 2
technique which uses high pressure (around 20−30 MPa) as

k 2{
a helping parameter with a relatively low temperature (around
600°) relative to conventional gasification (800−1000 °C). (i)

i xy
CHxOy + (1 − y)H 2O → CO + jjj1 − y + zzzH 2
The other significant advantage is the use of wet biomass, as

k 2{
the reaction occurs in the presence of water, thus requiring no
drying of biomass. Supercritical water gasification of biomass is (ii)
explained in the schematic diagram in Figure 22 and by the
following equations reported by Reddy et al.:134 Cellulose hydrolysis:
S DOI: 10.1021/acs.energyfuels.8b01678
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels Review

Figure 21. Schematic diagram of the hybrid gasification and fermentation system. Adapted with permission from ref 132. Copyright 2017 Elsevier.

Methanation reaction of CO:

CO + 3H 2 → CH4 + H 2O (viii)

Methanation reaction of CO2:

CO2 + 4H 2 → CH4 + 2H 2O (ix)

Hydrogenation reaction:
CO + 2H 2 → CH4 + 0.5O2 (x)
135
Kang et al. conducted supercritical water gasification for
waste biomass and concluded that the significant parameters
affecting the hydrogen production in decreasing order are as
follows: temperature > catalyst loading > catalyst type >
biomass type. A temperature around 650 °C and at 100%
catalyst loading produced the highest hydrogen. Nanda et al.136
produced a higher gas yield with nickel impregnated biomass
gasification than noncatalytic biomass gasification. The
optimum recommended conditions were 500 °C, biomass to
Figure 22. Biomass gasification under supercritical conditions. water ratio of 1:10, and 23−25 MPa with a 45 min residence
Catalysts A, B, C, and D represent Ni, Ru, Rh, Pt, Pd, Ni/Al2O3, time. The authors did not report the study at more than 500
Ni/C, Ru/Al2O3, and Ru/TiO2; Ni, Ru, Pt, and activated carbon; Ni, °C; however, increasing temperature seems to be more
Rh, Ru, Pt, and activated carbon; and Ni, Ru, NaOH, and KOH,
respectively. Reprinted with permission from ref 134. Copyright 2014
beneficial for higher hydrogen production. Figure 23 shows a
Elsevier. mechanism of glucose conversion during supercritical water
gasification treatment. Amrullah et al.137 recently conducted
(C6H12O5)n + nH 2O → nC6H12O6 (iii)
the SWG of sewage sludge in a continuous reactor in order to
convert the organic phosphorus present in sewage sludge into
Glucose reforming reaction: inorganic phosphorus. The inorganic phosphorus was obtained
C6H12O6 → 6CO + 6H 2 at a short residence time of 10 s in the reactor. This conversion
(iv)
of organic phosphorus to inorganic phosphorus required an
Hydrolysis of lignin: activation energy around 19.1 kJ/mol, and the remaining
inorganic phosphorus was further converted at 18.7 kJ/mol.
(C10H10O3)n + nH 2O → nC10H12O4 → Phenolics (v) Even though SWG contains several advantages toward
Steam reforming reaction: biofuel technology, there are, however, many disadvantages
which need to be explored further, for instance, impurity
Phenolics + H 2O → CO + CO2 + H 2 (vi) formation, economic inefficiency, clogging, and energy
Water−gas shift reaction: inefficiency. These critical factors diminish the positive aspects
of the process. Although recently some of the studies138,139
CO + H 2O → CO2 + H 2 (vii) reported positive results in order to reduce this barrier, a wide
T DOI: 10.1021/acs.energyfuels.8b01678
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
Figure 23. Supercritical water gasification of glucose at 400 °C. Reprinted with permission from ref 159. Copyright 2015 Elsevier.
study on different types of feedstock, however, is required to
optimize the efficient working parameters.
5. CONCLUSION
Biomass is a versatile feedstock and contains several merits
based on the technology utilized; however, combining the
biomass with coal or other kinds of wastes, for instance, plastic,
can be beneficial. The types of emissions and impurities
produced during thermal use contributed significantly to the
product’s effectiveness. The optimized parameters for each of
the technologies gives some sort of way out to reduce the
drawbacks associated with energy efficiency and unwanted
byproducts. Chemical looping combustion contains significant
advantages in reducing greenhouse gases and improving cost
efficiency. Moreover, co-combustion with coal or sewage
sludge increases the carbon conversion and capture efficiency.
Slagging and fouling during biomass combustion needs to be
re-evaluated according to the type of the biomass in a real time
scenario rather than depending on coal-based indices.
Pretreatment of biomass needs to be considered for Ca, Si,
and K prior to their use in heating technologies. Biomass ash
used as a fertilizer is recommended in the form of large tablets
to reduce the potassium release rate.
Pyrolysis products from biomass are widely regarded as
beneficial in many applications from wastewater treatment to
composites and from simple ethanol production to complex
upgraded biofuel production. Pyrolysis products typically need
to be treated further for appropriate use, either in the form of
upgrading of bio-oil or the activation of the char. The
upgradation mechanism needs to be thoroughly studied on
bio-oil rather than model compounds, which makes it difficult
to estimate the potential of the relevant technology.
U DOI: 10.1021/acs.energyfuels.8b01678
Review
Syngas use has been found in several applications due to its
instant use in engines, boilers, and electricity generators.
Hybrid systems are being researched extensively where the use
of syngas with other renewable fuels found positive results,
both for on- and off-grid supply of energy.
Although extensive research has been done in many areas of
biomass utilization, further research, however, is required in a
number of areas, for instance, refining and improving the
quality of biochemicals and reducing the water production
during fast pyrolysis. Multiple routes and integration of
different systems together required the preparation of one
efficient set of systems to use according to the type of biomass.
The development of new technologies is also inevitable due to
the limitations in the current systems. Thus, further research
will bring to a sustainable and environmentally friendly
approach of energy and biofuels generation closer.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: akhtar@ftz.czu.cz, akhtarczu@gmail.com.
ORCID
Ali Akhtar: 0000-0003-3141-2879
Notes
The authors declare no competing financial interest.
■ ABBREVIATIONS
CLC = chemical looping combustion
CO2 = carbon dioxide
CO = carbon monoxide
NOx = nitrogen oxides
SOx = sulfur oxides
GHG = greenhouse gases
UK = United Kingdom
Energy Fuels XXXX, XXX, XXX−XXX
Energy & Fuels
MSW = municipal solid waste
PM = particulate matter
kWh = kilowatt hour
SWG = supercritical water gasification
MW = megawatt
MJ/kg = megajoule per kilogram
■
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