10.1515 - Corrrev 2020 0095
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yonastegene63810.1515 - Corrrev 2020 0095
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yonastegene638Corros Rev 2021; 39(5): 387–408
Review
Shrutika Sharma*, Mayank Sharma, Deepa Mudgal and Hiralal Bhowmick
Adoption of strategies for clean combustion of
biomass in boilers
https://doi.org/10.1515/corrrev-2020-0095 1 Introduction
Received October 23, 2020; accepted July 28, 2021;
published online September 3, 2021
With increase in population, there is a continuous need to
secure energy, reduce wastage of non-renewable resources
Abstract: Fossil fuels like coal, oil and natural gas are
and utilize non-conventional sources of energy. Non-
continuously being used for electricity generation.
conventional sources of energy like solar energy, biomass
However, combustion of fossil fuels has raised environ-
and geothermal energy have the potential of energy genera-
mental concerns which have forced the world to search
tion in a sustainable and cleaner way, by which this source of
for alternative sources of energy like geothermal, solar
energy can be utilized by our future generations, without
and biomass energy. Biomass is a carbon-based fuel,
depletion of these renewable sources of energy (Olah et al.
readily available in many parts of the world, highly vol-
2018). For the conversion of energy into electricity, mostly
atile with less sulphur and nitrogen content, its ash
fossil fuels like coal, oil and natural gas are being used (Barma
possesses the property of absorbing carbon dioxide
et al. 2017). With an increase in demand, the consumption of
emissions, co-firing of biomass and coal increases ther-
fossil fuels is also increasing. However, it is expected that
mal efficiency, it creates employment opportunities and
these sources of energy might deplete in the coming years.
provides a better way of utilization of agricultural waste.
Also, the usage of fossil fuels is directly linked to carbon
However, chlorine species from biomass combustion re-
emissions that lead to environmental degradation. From 2009
sults in corrosion of boiler tubes at high temperature. In
to 2018, it was seen that 42% of carbon emissions were from
this review, challenges like fouling, agglomeration,
coal, 38% emissions from oil, 19% emissions from natural
gaseous emissions, emission of heavy metals, low heat-
gas, and 5% emissions from other sources (Peters et al. 2020).
ing value, storage and transportation problems and high
Due to the accumulation of carbon dioxide and other gases,
temperature corrosion have been discussed, which can
the greenhouse effect takes place which further leads to
limit the flexibility, economy and reliability of biomass
global warming. Fossil fuel combustion leads to the formation
boilers. Each of these challenges has a relatively satis-
of sulphur oxide and nitrous oxide resulting in acid rain and
factory solution except for hot corrosion, which has been
smog (Mahmoud et al. 2009). Due to all these environmental
addressed through several approaches with varying
effects, the need to search for renewable sources of energy
success and those approaches have been presented in
began to rise. Solar, geothermal and biomass energy have
this review. It is recommended that the implementation of
been selected as the alternative sources of energy with zero
the discussed remedies can surely provide efficient,
emission of carbon dioxide and other air pollutants.
economical and ecological biomass combustion.
Biomass refers to the organic materials derived from
Keywords: biomass-fuel; boilers; corrosion. plant and animal wastes (Demirbas 2010). It consists of
wood waste (sawdust, wooden pallets), woody crops (wil-
low, silver maple), agricultural wastes (rice husk, corn
waste), herbaceous crops (grass) and animal waste (cow
*Corresponding author: Shrutika Sharma, Department of Mechanical dung) (Demirbaş and Demirbaş 2003). India is dominated by
Engineering, Thapar Institute of Engineering and Technology, Patiala, agricultural and forestry industries and so, biomass can be
Punjab 147004, India, E-mail: shrutikasharma2009@gmail.com easily procured. Biomass mainly consists of cellulose, lignin
Mayank Sharma, Deepa Mudgal and Hiralal Bhowmick, Department of and hemicellulose. The amount of these constituents are
Mechanical Engineering, Thapar Institute of Engineering and
responsible for determining the heating value of biomass
Technology, Patiala, Punjab 147004, India, E-mail:
mayank.sharma1296@gmail.com (M. Sharma),
fuel (Zhang et al. 2010). Figure 1 shows carbon cycle of
deepa.mudgal@thapar.edu (D. Mudgal), biomass which explains that if biomass is fully combustible,
hiralal.bhowmick@thapar.edu (H. Bhowmick) the content of carbon dioxide produced on being burnt is
388 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
used as a fuel is highly volatile, reactive, and contains very
less carbon content (Demirbaş and Demirbaş 2003). It is an
eco-friendly and renewable fuel with less nitrogen and
sulphur content. Moreover, on the combustion of biomass,
the amount of carbon dioxide in the atmosphere remains
balanced. Also, if biomass is co-fired with coal, 93%
reduction in carbon dioxide has been reported, in com-
parison to the combustion of hard coal as alkaline ash from
biomass captures some of the sulphur dioxide and carbon
dioxide emissions produced during combustion (Saidur
et al. 2011). However, chlorine species from biomass result
in corrosion of boiler tubes and biomass deposits are bulky
and interfere in combustion so, proper cleaning is required
to remove them. Due to the high amount of volatile matter,
the ignition consistently takes place (Sami et al. 2001). The
ash released from this fuel has the property of absorbing
Figure 1: Carbon cycle of biomass explaining the carbon neutral
carbon dioxide and sulfur dioxide emissions (Saidur et al.
behavior of biomass. 2011). The nitrogen present in biomass can be converted to
ammonia during combustion, which can be used as
equal to that taken by biomass from atmosphere during its burning fuel. It is cheaper than fossil fuels and since it uses
growing stage. So, net addition of carbon dioxide is zero low-quality soil so, the degraded land has the possibility of
(Saidur et al. 2011).On the other hand, burning the same restoration. Agricultural waste can be utilized in a better
amount of fossil fuels results in the release of large quanti- way by converting it into biomass and our dependence on
ties of carbon dioxide in a short period. Moreover, when fossil fuels is also decreased. It has an added advantage of
biomass is left in an open atmosphere, it releases its energy being used with fossil fuels to reduce harmful emissions of
slowly resulting in wastage of energy. But, if biomass is carbon dioxide and nitrous oxide. It was reported that
burnt in the boiler, its energy can be utilized quickly for co-firing of biomass with coal resulted in thermal efficiency
steam generation and rotation of the turbine (Saidur et al. of 92% (Xu et al. 2020). Also, employment opportunities
2011; Tock et al. 2010). Table 1 discusses about the particle will be enhanced as labour would be required to harvest
sizes and bulk densities of various kinds of biomasses. The and transport biomass. Every source of energy offers some
biomass fuel can be chosen depending on these properties. disadvantages also which include low energy density and
Coal is used as a fuel in many power plants, however, high content of moisture. Because of the low energy den-
on comparison of biomass with coal, biomass has a density sity, the transportation cost is also high in order to avoid
of 500 kg/m3 whereas coal has a density of 1300 kg/m3. road congestion. High content of moisture reduces the
Biomass has carbon content of 42–54 wt% of dry fuel. It has stability of the flame. High amount of particulate matter is
an oxygen content of 35–45 wt% of dry fuel, which is released during its combustion due to which extra cost is
comparatively higher than that of coal (2–15 wt% of dry required to employ methods that reduce particulates.
fuel). The ignition temperature of biomass is between 418 Deforestation and biodiversity losses are also accompa-
and 426 K. It has a lower heating value of 14–21 MJ/kg, in nied by the usage of biomass as wooden pellets are pro-
comparison to that of coal (23–28 MJ/kg). Biomass when cured from forests which have resulted in deforestation in
Table : Particle size and bulk density of biomass fuels (Laboratory ).
Biomass fuel Particle size (m) Bulk density (kg/m)
Sawdust .–.
Chopped straw .–.
Greenwood chips .–.
Wood pellets .–.
Biomass briquettes .–.
Cordwood .–.
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 389
many parts of the world. Many energy companies cut 2 Method
mature trees for obtaining forest timber to be used as bio-
fuel for biomass plants. This results in deforestation, soil The literature for review was selected in two steps: (1) literature was
erosion, habitat loss and destruction of natural beauty identified based on keywords and relevant literature was selected
(Sage 2019). When incineration of waste takes place, toxic based on some rules, and (2) final literature was extracted based on the
ash is released into the air, which settles on the ground, topics and information discussed in the literature.
thus, polluting groundwater. Corrosion at high tempera-
ture takes place due to the presence of chlorine in biomass 2.1 Literature identification
(De Best et al. 2008; Demirbaş 2003; Vassilev et al. 2010;
Yusuf 2011). Figure 2 shows biomass fired boiler with Literature was searched on Google Scholar and Science Direct with the
various components and wood as fuel. help of keywords like “problems on combustion of biomass”, “biomass
as a fuel for boilers”, “advantages and disadvantages of biomass”,
From the characteristics of biomass and its combus-
“recent trends on biomass usage” and “potential of biomass to be used
tion, it has been found that it provides many social, as a source of energy”. The literature that was obtained gave some
economical and environmental benefits such as conser- introduction about the topic and all the problems of biomass were
vation of non-renewable fossil fuels, employment op- noted. After this, literature was searched for each problem with the help
portunities, financial saving due to low cost and of keywords like “fouling”, “agglomeration”, “emission of heavy
metals”, “gaseous emissions”, “low heating value of biomass”, “stor-
reduction in emissions of carbon dioxide and sulphur
age and transportation problem of biomass” and “high-temperature
oxide emissions. However, combustion of biomass can corrosion on using biomass as a fuel for boilers”. The literature obtained
lead to issues like fouling, agglomeration, emission of by each of these keywords gave an insight about the description of the
heavy metals, low heating value, storage problems and problem. Then solutions were searched for each problem and the main
hot corrosion due to chlorine species present in biomass. focus was drawn on searching the latest solutions for each problem. The
latest solutions were searched by entering the year of research and
Hot corrosion has been responsible for causing shutdown
results were obtained for solutions of problems that were researched
of biomass boilers, reducing boiler efficiency and and published in the years 2018, 2019, and 2020.
increasing productivity losses. Rules that were used as exclusion criteria for the purpose of
Currently, biomass is being used for the generation of literature review are as follows: 1) papers published before 2000 were
electricity, household heating, cooking purposes, fueling excluded from the literature review; 2) papers in which biomass was
burnt in coal-fired boilers were excluded.
of vehicles and providing heat for industrial processes. It
can be used in boilers for combustion. Challenges related
2.2 Final literature
to biomass combustion can limit the reliability of biomass
so, this review addresses solutions for challenges that are
After the selection of initial literature, the content of all the research
encountered in boilers due to the burning of biomass. The
papers was carefully read. Depending on the objective of its research,
successful implementation of these solutions can make methods used, type of biomass used, the material of boiler tubes and
biomass boilers more efficient and cost-effective (Saidur solutions are drawn to solve the problem, the papers were selected for
et al. 2011). the final literature review.
Figure 2: Biomass fired boiler (Hub 2018).
390 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
3 Combustion of biomass in boilers agglomeration, emissions of heavy metals, gaseous
emissions (CO, NOx, N2O, SOx), low heating value, stor-
Although, biomass is environment friendly but the usage age and transportation problems and high-temperature
of this fuel results in many problems that lead to a sud- corrosion (Singh et al. 2018). The problems encountered
den interruption in the working of boilers and additional in biomass combustion and their remedies are summa-
cost of repairing. These problems include fouling, rized in the table as follows (Table 2):
Table : Problems and solutions for combustion of biomass in boilers.
S. Problems Remedies References
no.
. Fouling (a) Leaching or pre-treatment of biomass with water Gudka et al. () and Melissari ()
(b) Optimization of airflow rate and deposition probe Febrero et al. ()
temperature
(c) Hybrid system design (neural networks and fuzzy Romeo and Gareta ()
logic system)
(d) Reduction of adhesion force by thermal spray Naganuma et al. ()
coatings
(e) Reducing the content of potassium with the help Liao et al. ()
of additives
(f) Reducing the content of chlorides with the help of Kassman et al. ()
ammonium sulfate
. Agglomeration (a) Optimization of bed temperature, fluidization ve- Lin et al. ()
locity and size of bed particles
(b) Proper selection of bed materials Brus et al. (), De Geyter et al. (), Fernández Llorente
et al. (), Grimm et al. (), and Silvennoinen ()
(c) Change in reactor design Bartels et al. ()
(d) Usage of additives in normal silica sand Corcoran et al. () and Davidsson et al. ()
. Emission of heavy Absorption using silicates and aluminosilicates, Khan et al. ()
metals adsorption using activated carbon and ion-exchange
process, disposal to landfill
. Gaseous emissions (a) Design of longer freeboards, reaction with Khan et al. (), Lamberg et al. ()
(CO, NOx, NO, SOx) ammonia
(b) Air staging Khan et al. (), Liu et al. (), and Zabetta et al. ()
(c) Selective non-catalyst reduction, usage of ultra- Cai et al. (), Grosso et al. (), and Mladenović et al.
fine limestone ()
. Low heating value (a) Usage of fuel with high extractive content Demirbas and Demirbas ()
(b) Torrefaction, densification techniques and hy- Kambo and Dutta (), Keipi et al. (), and Wattananoi
drothermal carbonization et al. ()
(c) Liquid hot water treatment Runge et al. ()
(d) Proximate analysis using artificial neural network Uzun et al. ()
. Storage and trans- (a) Setting up of intermediate storage facility Rentizelas et al. ()
portation problems (b) Terminal site for continuous quality up-gradation Gautam et al. ()
(c) Model for fire risk reduction Shabani and Sowlati ()
(d) Usage of mixed transport, pipelines Flodén and Williamsson () and Malladi and Sowlati
()
(e) Preprocessing of biomass at intermediate storage Flisberg et al. ()
location
. High temperature (a) Use of superalloys and high chromium steel as Cho et al. (), Gao et al. (), Gupta et al. (),
corrosion materials for boiler tubes (Super H, Superni , Kamal et al. (), Luo et al. (), Mishra et al. (),
Superni , superfer H, Superni , Superni , Mlonka-Mędrala et al. (), Mudgal et al. (), and
NiAl based alloy IC, nickel based N) Zhao et al. ()
(b) Application of thermal coatings to boiler materials Agüero et al. (), Bignal et al. (), Brus et al. (),
and superalloys (NiCr, CrO, CrC–NiCr, Demirbas (a), Demirbaş (b), Grimm et al. (),
NiCrAlY, Ni–Al, NiCrAl, Fe–Cr) Hearley et al. (), Hussain et al. (, ), James et
al. (), Khan et al. (), Mahesh et al. (a,b),
Nawrot et al. (), Ohman and Nordin (), Oksa et al.
(), Prashanth et al. (), Visser (), and Visser et
al. ()
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 391
Further, each of these problems has been discussed, in Another way for reduced fouling is the design of a
detail, along with the ways of overcoming them. hybrid system using neural networks and the Fuzzy Logic
Expert System (Table 2), which is responsible for simula-
tion, prediction, and control of soot blowing cycles. It
3.1 Fouling
performed thermal monitoring, fouling or deposit predic-
tion, analysis of boiler behavior, and finding the number
3.1.1 Description
and timing of soot blowing cycles. The system will suggest
a certain number of soot blowing cycles and the rest of
Fouling, also known as deposits, refers to the deposition of
them will be done automatically. This method not only
ash on heat transfer tubes. Sulfur, chlorine and silicon are
reduces fouling but also helps in energy saving. On the
responsible for increasing the volatility of sodium and
implementation of this system, 3.5% of energy can be
potassium (alkali compounds). These alkali compounds
saved (Romeo and Gareta 2009).
combine with chlorine to form alkali chlorides, which
The mechanism of fouling was studied and it was
escape in the form of gas. Flue gases on cooling, deposit on
found that alkali sulfates play an important role in
heat exchanger tubes. In the presence of silicon, alkali
increasing the adhesion force. The reduction of adhesion
silicates are formed; having low melting temperature,
force can be a solution to fouling. So, nickel alloy thermal
leave a sticky surface for increased deposition. The non-
spray coating can be done on boiler tubes, which helps in
volatile compounds present in the fuel form ash, which
reducing adhesion force (Table 2) (Naganuma et al. 2013).
consists of elements like magnesium, calcium, silicon with
small amounts of sodium, potassium and aluminium Reducing the content of potassium can also be a
(Altobelli et al. 2013). Coarse particles are found as deposits solution to fouling, as mentioned in Table 2. Composite
on surfaces of the heat exchanger. Potassium reacts with additive with 20–50% blowing air, 25–65% kaolin,
calcium and silicate present in ash to form a glassy struc- 20–60% MgO, and 15–30% activated alumina reduced the
ture, which is responsible for heavy deposits. Thus, fouling content of potassium and so, fouling was also reduced.
or deposits lead to decreased boiler efficiency and heat With an increase in combustion temperature, the additives
transfer. They also result in increased operating cost, car- worked in a better way and CaO can be added to reduce the
bon monoxide and nitrogen oxide emissions (Demirbas emission of HCl (Liao et al. 2015).
2005a; Jiménez and Ballester 2007; Khan et al. 2009). Chlorides are very harmful to biomass boilers and so,
strategies can be adopted to reduce the content of chlorides
3.1.2 Solutions (Table 2). Ammonium sulfate can be used as an additive for
the conversion of KCl to its sulfate through which, the
Through leaching or pre-treatment of biomass with water, chloride content can be highly reduced. Combustion of
the ash content can be reduced (Table 2). With an increase biomass with peat can also be a strategy for the reduction
in temperature of the water used for pre-treatment, the of chlorides. Components like aluminium, sodium, and
melting point of ash increases, which eventually improves calcium present in peat ash are responsible for capturing
the efficiency of the combustion process. The content of potassium and converting its chloride into sulfate (Kass-
chlorine, potassium, sodium and sulfur can be reduced by man et al. 2013).
30–100%, 50–90%, 10–90% and 0–95% respectively. The
concentration of silicon, titanium and aluminium can be
reduced by 15% with the help of cold washing. Reduction 3.2 Agglomeration
in concentrations of the above-mentioned elements can
reduce fouling (Gudka et al. 2016; Melissari 2017). 3.2.1 Description
The second way of reducing fouling in wooden biomass
is through the optimization of airflow rate and deposition Agglomeration results when particles of ash form layers
probe temperature (Table 2). When the airflow rate and around particles of bed material (mostly quartz sand). It
probe temperature are increased from 11 to 25 m3/h and takes place due to chemical reactions, liquid phase pres-
25–65 °C respectively, the amount of unburnt carbon can be ence, and solid-state sintering. If the melt or ash is highly
reduced. Many non-volatile compounds like calcium, mag- viscous, it gives a glassy structure, which on cooling, does
nesium, silicon, aluminium, and titanium remain in the ash not crystallize. If the melt is less viscous, the alkali com-
but the content of sulfur can be reduced to a great extent. pounds melt increasing the stickiness of the particles. The
The content of chlorine should be reduced in the biomass to alkali compounds act like bonding agents, thus, enhancing
reduce its deposition on boiler tubes (Febrero et al. 2015). agglomeration (Llorente et al. 2006). The chemical reaction
392 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
includes the reaction of potassium phosphate with either of silicate compounds with low melting points whereas
silicon or calcium, which results in silicates of potassium olivine contains silica, calcium, and magnesium (respon-
and calcium with a low melting point. sible for increasing the melting temperature of potassium
In fluidized biomass boilers, the main cause of silicate). Results have shown that agglomeration was lesser
agglomeration is the partial melting of inorganic com- in the case of olivine bed material in comparison to quartz
pounds. In an agglomerated bed particle, the inner layers sand (Brus et al. 2004; De Geyter et al. 2007; Grimm et al.
have a composition similar to that of the bed material and 2012). Limestone of particle size 0.25–2 mm with fluidization
the outer layers have a composition similar to that of the velocity of 1.2 m/s has shown lesser agglomeration deposits
fuel. Two phenomena have been studied: melt-induced than silica sand when used as bed material. In the case of
agglomeration and coating induced agglomeration. In melt- limestone, calcium carbonate, calcium oxide, and calcium
induced agglomeration, the bed particles adhere to each hydroxide escape bed material to reduce ash deposits on
other due to high local temperature and on the other hand, a boiler tubes (Fernández Llorente et al. 2006). Other bed
uniform coating is present on particles of bed material. In materials like alumina, ferrite oxide, and dolomite have
this coating, the formation of neck starts and as this neck problems related to chemical stability. Agglostop can be
formation continues, a high-temperature zone forms which used as bed material because it can handle alkali related
help in melt formation, thus, promoting agglomeration agglomeration problems (Silvennoinen 2019).
(Melissari 2017; Visser 2004; Visser et al. 2008). Change in reactor design can also be a solution to this
According to Ohman et al. (2000), the deposition of ash problem by implementing a stirrer to break up agglomer-
on bed material is a combination of processes that include: ates (which can break easily) or by passing a high-velocity
attachment of small particles on grains of bed material gas stream or by using the concept of the hydro-beam floor
followed by condensation of alkali compounds (potas- in which coarse bed particles are removed repeatedly
sium, potassium chloride, and potassium sulfate) followed (Table 2) (Bartels et al. 2008).
by reaction of alkali compounds with the bed material Another alternative to reduce agglomeration is the
surface. On deposition, each inner layer undergoes sin- usage of additives in normal silica sand (Table 2). Kaolin
tering and gets strengthened. Agglomeration takes place can reduce the concentration of potassium chloride and so,
due to any of the three mechanisms. First, due to the re- agglomeration can be reduced. But, kaolin is so expensive
action between bed material and alkali compounds, so, it can be replaced by ammonium sulfate, which gives
potassium silicate is formed which promotes the formation the highest efficiency and is most effective in the elimina-
of bed layers. Second, the reaction takes place directly tion of agglomeration, after kaolin (Davidsson et al. 2008).
between gaseous potassium and bed material particles, Other additives like dolomite and alumina can also be used
which results in the formation of potassium silicate that which do not allow reaction between potassium and silica.
initiates agglomeration. Third, adhesion of bed particles by Ilmenite has the advantage of absorbing potassium parti-
partially melted potassium silicate and potassium- cles from ash, thus, reducing agglomeration when used
calcium/magnesium phosphates from fuel (Brus et al. with sand bed material (Corcoran et al. 2014).
2005; Grimm et al. 2011). Operating parameters can be altered to control the
It has been reported that biomass with herbaceous problem of agglomeration, as mentioned in Table 2. Lower
materials results in increased agglomeration due to the high bed temperature, higher fluidization velocity, and finer bed
concentration of alkali compounds. Alkali compounds like particles are ideal for reduced agglomeration. Lower bed
potassium, calcium, magnesium, silicon, and aluminium temperature reduces the ash-melting rate. When the velocity
are highly responsible for agglomeration problems. The of the gas is high, defluidization time is more and so,
bottom ash captures vaporized potassium, which combines breaking of agglomerates can take place easily. With finer
with silica present in bed material leading to agglomeration bed particles, the defluidization time is more (Lin et al. 2003).
(Lin et al. 2003; Llorente et al. 2006). Biomass has a bright
future and so, it is important to control the problem of
agglomeration since eliminating it is not possible. 3.3 Emissions of heavy metals
3.2.2 Solutions 3.3.1 Description
The selection of bed materials can help in reducing Heavy metals like arsenic, cadmium, arsenic and lead are
agglomeration (Table 2). Quartz sand contains silica, highly toxic for the environment that are released during
potassium, and calcium and is responsible for the formation burning of biomass. Low quantities of copper, zinc, cobalt,
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 393
selenium, nickel and manganese are required by human can be disposed to a landfill (Table 2) (Khan et al. 2009). To
body for molecular and biological functions but large reduce the amount of ash that is deposited to the landfill,
quantities of these heavy metals given out in the form of ash sieve fractionation method should be preferred to reduce the
during biomass combustion pose a threat to the environ- amount of unburnt carbon present in the ash and followed
ment (Prashanth et al. 2015). The concentration of these by gasification process for removal of highly important ele-
heavy metals depends on the source of biomass and how far ments that should not go to the landfill and get leached with
is it from the source of pollution. Heavy metals are usually surrounding environment (James et al. 2012).These pro-
found in fuel ash with particles smaller than 1 μm. Moreover, cesses basically separate out the solid unburnt and harmful
their concentration increases with the decreasing tempera- soluble compounds from fly-ash.
ture of precipitation and the size of the particle (Demirbas
2008; Demirbaş 2005b). Cadmium as heavy metal is harmful
to humans as it accumulates in the kidneys and causes 3.4 Gaseous emissions (CO, NOx, N2O, SOx)
cancer. Lead is also a toxic metal that is harmful to the brain
even at low concentrations (Nawrot et al. 2006). 3.4.1 Description
In the boiler, metals like cadmium, argon, zinc, and lead
volatilize in the form of oxides and chlorides and deposit in the Emissions from biomass generally include CO, NOx, N2O
form of ash. During combustion, cadmium, and lead vapourize and SOx emissions.
in the form of cadmium chloride and lead chloride respec- CO emissions are usually a result of incomplete
tively. Although zinc is present in fuel ash in its stable form, but burning, excess air, shorter residence time, low tempera-
the small amount of zinc gets converted to zinc chloride. Thus, ture, and high concentration of carbon content in the fuel. A
sublime metal is passed on to fly-ash with the help of chlorine. sudden decrease in the temperature of the flame and poor
Non-volatile metals such as aluminium, copper, and iron are mixing of fuel with air often leads to increased CO emissions.
found in coarse fly-ash because they are converted to oxide The main reason for CO emissions is the usage of the boiler
form which is very stable (Khan et al. 2009). Some heavy that was once used for coal combustion and has undergone
metals like selenium and mercury escape the biomass boiler in no modification for the combustion of biomass. A large
the form of gases from flue gas outlet. Workers may be exposed amount of volatile matter is present in biomass which re-
to gaseous pollutants and particulate matter generated from quires longer freeboards for longer residence time, which is
biomass handling, transportation, storage and ash generated sometimes not provided by small-scale industries, resulting
from post combustion processes like cleaning of flue gases and in high CO emissions. Also, heat exchangers decrease the
removal of carbon dioxide. Trucker is involved in trans- temperature of the boiler due to which carbon monoxide
portation of ash, fuel handling operative is involved in storage cannot be fully converted to carbon dioxide. It has been
of biomass leading to exposure to off-gases from storage reported that high moisture content, low boiler demand, the
chamber, cleaner is involved in removal of deposits from plant, large size of fuel particle and high ash content are respon-
maintenance engineer is involved in maintenance of boiler sible for high CO emissions (Bignal et al. 2008; Demirbas
leading to exposure to combustion gases and ash handling 2005a; Khan et al. 2005, 2009).
operative is involved in ash removal and its transportation to NOx emissions include nitrogen oxide and nitrogen
ash storage chamber (Rohr et al. 2015). dioxide, which are responsible for the formation of smog,
particulate matter, and acid rain. Volatile matter consists
3.3.2 Solutions of nitrogen-containing species (NH3 and HCN) which
oxidize to form NOx. These emissions do not depend much
The presence of heavy metals in fly-ash is a serious prob- on the operating conditions of the boiler but mostly depend
lem for which the following measures can be taken. on the nitrogen content present in the fuel, amount of
For control of heavy metals, absorption of lead and available oxygen for combustion, and fuel reactivity. High
cadmium with absorbents like silicates and aluminosilicates moisture content and improper dosage of fuel result in high
has proved to be very effective (Table 2). The chemical re- NOx emissions. Proper regulation of oxygen also plays an
action of heavy metals with adsorbents like alumina, silica, important role in NOx emissions (Khan et al. 2009; Vitázek
and bauxite can also be one of the solutions. Methods like et al. 2016).
adsorption using activated carbon, ion-exchange process, N2O oxidizes into NO in the presence of sunlight which
and post precipitation can also be employed to reduce heavy further causes depletion of the ozone layer. Biomass fuel
metal emissions to a great extent (Table 2). For the metal composition plays an important role. On the combustion of
concentrated ash to not cause any harm to the boiler tubes, it biomass, the more is the production of cyano species, the
394 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
more are N2O emissions and on the other hand, the pro- the post-combustion chamber and ammonia can continue
duction of NH3 results in lower N2O emissions. These as a reducing agent in selective catalyst reduction (Table 2).
emissions greatly depend on boiler temperature and This hybrid technique has been reported as the most suc-
excess air supply. At high temperature, N2O converts into cessful one for N2O reduction. Recently, the usage of ultra-
N2, and thus, high temperature is suitable for N2O reduc- fine limestone with a particle size of 20 μm has emerged as
tion, and on the supply of excess air, there is a decrease in an innovative solution for the reduction of N2O and SOx
temperature which increases the formation of NO and N2O. emissions (Table 2). The content of ultra-fine limestone
From the literature, it has been observed that biomass needs to be optimized for nitrogenous emissions (Cai et al.
combustion results in lower N2O emissions than coal and 2019; Grosso et al. 2009; Mladenović et al. 2003). With the
natural gas (Bai et al. 2013; Khan et al. 2009). increase in particle size of limestone, the efficiency of
SOx emissions include SO2, SO3, and other alkali sul- desulphurization decreases, which results in increased SOx
fates, which react with chlorine resulting in corrosion of emissions.
boiler tubes. In the boiler, at the time of flue gas cooling,
the sulfates get deposited on the surfaces. It has been re-
ported that on using biomass with coal, SO2 emissions can 3.5 Low heating value
be reduced because of the presence of calcium oxide and
magnesium oxide that can absorb SO2 emissions (Khan 3.5.1 Description
et al. 2009; Williams et al. 2012).
The heating value of biomass can be defined based on high
3.4.2 Solutions heating value (HHV) which is the overall heat content of the
fuel. Low heating value can be obtained by subtracting the
Gaseous emissions play a major role in polluting the amount of energy required to remove the moisture content of
environment, so, the issue of release of gaseous emissions biomass. This low heating value of biomass can be attributed
needs to be resolved. One of the solutions to reduce carbon to low density, high moisture, and oxygen content. Due to
monoxide emissions can be the design of longer free- this, biomass experiences problems in flame stability. Coal
boards which can increase the residence time of biomass in has a higher heating value (23–28 MJ/kg) in comparison to
the boiler for its proper combustion (Table 2). The heat biomass (14–21 MJ/kg). It has been reported that compounds
exchanger present in the freeboard should also be containing carbon and hydrogen tend to increase the heating
removed as a heat exchanger decreases the temperature value of biomass while oxygen tends to decrease it. When
which is not suitable for CO emission reduction. Air staging compared to lignin, it has been observed that hemicellulose
and boiler load should be optimized according to the and cellulose present in biomass have lower heating value
carbon content in the fuel. Selective catalyst reduction is a due to their oxidation. Ash content is also a major factor
successful method of reducing CO and NOx emissions responsible for low heating value, thus, making its combus-
(Table 2). Reagent like ammonia is used which reacts with tion inefficient (Demirbas 2005b; Khan et al. 2009; Saidur
NOx and CO in the presence of a catalyst which oxidizes CO et al. 2011).
to carbon dioxide and reduces NOx to nitrogen. By this
process, CO emissions are reduced by 70–85%, and NOx 3.5.2 Solutions
emissions are reduced by 70–95% (Khan et al. 2008;
Lamberg et al. 2011). Air staging is also an effective solu- One of the solutions to increase the heating value can the
tion for the reduction of NOx emissions, which prevents the usage of fuel with high extractive content. Wood has a high
insufficient supply of fuel and oxygen for proper com- concentration of extractives which directly affects the
bustion (Table 2). This inhibits the chemical reaction of heating value of the fuel. It has been reported that ex-
nitrogen being converted to NOx. The secondary air inlet, tractives play an important role in increasing the heating
when placed above the fuel bed, has proved to reduce NOx value, thus, making the fuel desirable for combustion
emissions significantly. Proper mixing between primary (Table 2) (Demirbas and Demirbas 2009).
and secondary combustion zone products can reduce Torrefaction and densification techniques have proved to
gaseous emissions to a great extent. The type of biomass be advantageous in improving the heating value of the fuel
fuel can also be changed with wood being used as biomass (Table 2). Torrefaction is a process in which biomass, in the
fuel because of its low sulfur and nitrogen content, form of chips or crushed, is fed for pyrolysis in an inert at-
resulting in reduced gaseous emissions (Khan et al. 2009; mosphere at 200–300 °C which results in fuel with better-
Liu et al. 2013; Zabetta et al. 2005). grinding properties and high carbon content. The solid fuels
The selective non-catalyst reduction can play a major with a heating value of 21 MJ/kg had a significant increase in
role in the reduction of N2O emissions with feeding urea in their heating value (23.2 MJ/kg) after a torrefaction time of
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 395
60 min. The torrefaction time needs to be optimized as after biomass, a huge amount of material is required for a consid-
some time, it does not affect the heating value. Moreover, this erable amount of energy. Storage can be done at supply, in-
process can reduce the chlorine content of fuel up to 90% with termediate, and conversion sites but supply and conversion
results in reduced ash content. With an increase in torrefaction sites are usually time-constrained for agricultural and wood
temperature, the carbon and hydrogen contents increase in a residues, therefore, intermediate storage is often preferred for
significant amount, and oxygen content is reduced. After tor- them. Forest residues and remain in forests for several months
refaction, often densification is done in pellet mills to increase during which open-air drying takes place. On storage, it was
the density of the biomass fuel, which eventually increases the noticed that internal heat generation and decay of biomass
heating value of the same, thus, improving the combustion can lead to fire so, it is necessary to take measures for solving
properties. Hydrothermal carbonization is also a pre-treatment storage and transportation problems (He et al. 2014; Malladi
method that has a better effect on fuel properties than torre- and Sowlati 2018, 2017; Rentizelas et al. 2009).
faction (Table 2). The durability and density of fuels under-
going hydrothermal carbonization decrease with increasing 3.6.2 Solutions
temperature. When miscanthus was used as a fuel, this pro-
cess was highly effective in reducing the concentration of al- Setting up of intermediate storage facility close to the power
kali metals, ash content, and increasing the carbon content, plant can be one of the solutions to handling storage prob-
resulting in the increased heating value of the fuel (Kambo and lems (Table 2). The moisture content can be reduced to an
Dutta 2014; Keipi et al. 2014; Wattananoi et al. 2011). acceptable level with no formation of fungus and spores. The
Liquid hot water treatment has also proved to be an energy of biomass can be converted efficiently with reduced
effective solution for increasing the heating value of the fuel transportation costs. Usually, biomass that is collected from
(Table 2). Hot water treatment results in increased heating fields contains high amount of moisture and needs to be
value with a density increase of 16–25%. An increase in dried in storage facilities before using as a fuel for biomass
density increases the forces between molecules so that more boilers. Drying of biomass usually takes place by external
heat is required to break those forces (Runge et al. 2013). drying process which involves the use of hot air as an input.
Proximate analysis using the artificial neural network So, biomass containing low moisture can be dried using
can also be used to predict the heating values of different external drying process and will cause no degradation of
fuels depending on their compositions and accordingly, the biomass during the drying process. But, biomass containing
fuel can be changed for increased heating value (Table 2) high amounts of moisture can be degraded with time so, this
(Uzun et al. 2017). process is not favorable for biomass containing high mois-
ture content due to the risk of biomass degradation (Rent-
izelas et al. 2009). Other solutions can be adopted for
3.6 Storage and transportation problems biomass with high moisture content
A terminal site can be made in between the supply and
3.6.1 Description conversion sites where continuous quality up-gradation
can take place which would prevent deterioration of the
The storage problem is directly linked to the moisture content biomass and this terminal site can provide biomass in
present in the biomass. Biomass fuels with low moisture varied seasons (Table 2). 4–11% of moisture content can be
content (around 15–20%) can be stored without drying but removed from biomass at this terminal site. The model has
biomass fuels with high moisture content (around 40–50%) been designed which performs calculations on the amount
must be dried before storage otherwise it leads to deterioration of biomass which is to be supplied from open-air storage to
of biomass, fire risks and loss of useful energy. Often, biomass closed shed storage and the amount of biomass that is to be
is left open on fields for drying which does not reduce its stored in each storage (Gautam et al. 2017).
moisture content to an acceptable level and also leads to loss A model has been made to reduce the risk of fire when
of material. The farmers working nearby may experience the amount of biomass exceeds the limit (Table 2). When
serious health issues due to the formation of fungus and storage is more than the prescribed limit, the model applies
spores. Farmers are required to prepare the land for the next extra handling and personnel charges so that proper care is
crop and so, they hardly allow storage of biomass on open given to biomass, resulting in reduced risk of fire (Shabani
fields. Storage at intermediate places also results in increased and Sowlati 2013).
transportation cost due to transportation of biomass from To reduce transportation costs, mixed transport can be
source to intermediate place and then from that storage place used which may include transportation from the supply
to the power plant. Moreover, due to the low density of site to the intermediate site through trains, and then final
396 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
transportation from the intermediate site to the conver- (Table 2). Another solution for corrosion reduction can be
sions site can be through trucks (Table 2). Pipelines can the implementation of techniques, for reducing chlorine
also be used for long-distance transportation of biomass content present in biomass, which includes pre-treatment,
mixed with carrying fluid like oil or water but it results in adsorption, and absorption using various chemicals as
the reduced heating value of biomass (Flodén and Wil- discussed above. Table 3 shows the chemical composition
liamsson 2016; Malladi and Sowlati 2018). of alloys used in this literature.
Pre-processing of biomass is another solution for effi- Failure usually takes place due to residual stresses
cient storage and transportation because pre-processing of and intergranular corrosion so, Gao et al. (Gao et al. 2012)
agricultural and forest residues results in increased density developed a novel stainless steel Super 304H with high-
which reduces storage and transportation costs (Table 2). Pre- temperature strength and excellent corrosion resistance.
processing includes the conversion of agricultural residues Boiler tubes made with this material have proved to be
into bales, forest residues undergo chipping and grinding. corrosion resistant. Superalloy C22 when tested as
The pre-processing of biomass at intermediate storage loca- superheater material, in 80 wt% KCl + 20 wt% K2SO4 for
tions has proved to be highly efficient (Flisberg et al. 2015). 218 h, has shown best corrosion resistance due to stable
nickel, iron and chromium oxides present on it, which
were responsible for corrosion-resistant behavior (Luo
3.7 High-temperature corrosion et al. 2012). On comparing the corrosion resistance of
Superni 718 and Superni 76, it was observed that Superni
3.7.1 Description 76 showed better corrosion resistance due to the presence
of chromium oxide, ferrous oxide and NiO. This superal-
Corrosion is a serious problem due to which rupture and loy, when tested at 900 °C in Na2SO4 + 60% V2O5, gave the
thinning of boiler tubes takes place resulting in an un- best corrosion resistance out of Superni 718 and Superfer
wanted shutdown of boilers. Superheater, reheater, 800H due to the presence of protective oxides. Thus,
economizer, and air preheater are often at the risk of Superni 76 can be used as boiler tube material (Gupta
corrosion (Kawahara 2016b). In comparison to fossil fuels, et al. 2012; Kamal et al. 2010). Ni3Al based alloys have also
biomass contains higher amounts of alkali metals, ash shown good corrosion resistant properties with IC21
content and moisture. On the combustion of biomass, having the best corrosion resistance out of IC32 and IC6.
alkali metals are often vaporized in the form of salts Ni3Al based IC21 is favorable for its usage in the salt
containing sulfur, silicon, potassium, and chlorine, environment of the boiler, with the addition of yttrium
which are highly corrosive (Jiamin and Zhansong 2009). and chromium which are responsible for improving the
With boilers operating at a temperature of 750 °C, these corrosion resistance of IC21 alloy. Nickel-based N07263
salts get deposited on boiler tubes. The tubes used in has shown good corrosion resistance in the presence of
boilers are such that they form a protective oxide layer on salts due to its dense, adherent and continuous layer on
them at high temperatures. On the deposition of these surfaces (Cho et al. 2012; Zhao et al. 2014). When super-
salts, the oxide layer dissolves, thus, leaving the boiler alloys like Superni 75, Superni 600, Superni 718 and
tubes unprotected. When moisture present in biomass superfer 800 were placed in a boiler environment at 540 °C
reacts with unprotected surfaces, it leads to high- for 1000 h, maximum weight loss was observed for
temperature corrosion which degrades the surfaces, Superni 600 and minimum weight loss was observed for
resulting in combustion inefficiency and ineffectiveness Superni 718. Fly-ash particles often deposit on superalloy
(Coleman et al. 2008; Demirbas 2005a; Fauchais and surfaces, forming oxides which further prevent penetra-
Vardelle 2012; Mahajan and Chhibber 2019; Oksa et al. tion of other particles, thus, forming a protective layer
2014a; Yuan and Wang 2010). against corrosive species (Mishra et al. 2014).
Coatings on superalloys and other substrates have
3.7.2 Solutions come up as an economical solution for controlling high-
temperature corrosion (Kaur et al. 2008). Usually, the cost
From the literature, mainly two solutions have come up to is very high on changing the material of boiler tubes and
control corrosion. First is the use of superalloys as a so, coatings are mostly preferred. On detonation spray of
material for boiler tubes (Table 2). The second solution is 75Ni25Cr on 347HSS, the coating remained intact to the
the application of thermal coatings, by different thermal substrate with less metal loss in comparison to that of the
spray techniques, on the existing material of boiler tubes bare sample. Cr2O3, K2CrO4 and NiCr2O4 oxides were
(Kalivodova et al. 2005; Sidhu et al. 2006; Zhang et al. 2020) responsible for corrosion resistance while iron oxides
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 397
failed to serve the purpose because of their porous nature
Re
(Gada et al. 2019). The application of chromium oxide
V
.
coating (plasma-sprayed) on SA213-T22 alloy has helped
in preventing cracks, spalling, scales and weight gain
W
during corrosion at 850 °C. Apart from chromium oxide,
Co
.
.
.
Cr3C2–25NiCr (HVOF sprayed) has also reduced corrosion
of base material by the formation of protective oxides with
B
<.
a 25% decrease in corrosion after application of the
coating. The addition of molybdenum and aluminium to
nickel-based HVOF coatings enhanced the high-temperature
.
.
.
.
.
.
P
corrosion resistance of the substrate. The coating of NiCr on
ASTM-SA210 Grade A1 alloy gives the best corrosion resis-
<.
.
.
.
.
.
S
tance while WC-Co coating gives the worst corrosion
resistance. Chromium rich oxide scale due to Cr3C2–NiCr
coating has contributed to corrosion reduction on SAE-347H
N
.
steel at 700 °C (Kaur et al. 2009, 2012; Oksa et al. 2014a; Singh
.
.
.
.
Al
et al. 2006, 2017).
Coatings can also be applied to superalloys to
.
Ta
enhance their corrosion-resistant behavior. Superni 76
has already proved to increase the corrosion resistance
Elements (wt%)
.
.
.
.
.
.
.
.
.–.
.–.
.
of boiler steel but the application of NiCrAlY coating can
further improve the corrosion resistance of superalloy by
forming a continuous layer of aluminium oxide (Rana
et al. 2014). The corrosion resistance of Superfer 800 can
.
.
.
.
Ti
.
be increased by the application of either Ni–5Al or NiCrAl
Si
.
.
.
.
.
.
.
coatings through HVOF spraying technique, which leads
to the formation of aluminium and chromium oxides,
.
.
.
.
.–.
Mo
preventing further penetration of corrosive species
(Mahesh et al. 2008a,b). For improving corrosion resis-
tance of Cr3C2–25NiCr coated Superni 600, ceria oxide
can be added to Cr3C2–25NiCr in an optimum weight
Cu
.
.
percentage, leading to the formation of CeO2 and CeS,
which are responsible for reducing porous scale and
Cr
.
.
.
.
.
.
–
.–.
weight loss in bare Superni 600 (Kamal et al. 2008;
Mudgal et al. 2014a). On addition of ceria oxide, along
with CeO2 and CeS, the formation of Cr2O3, NiCr2O4, NiS
Mn
.
.
.
.
.
.
.
.–.
.–.
.
and Ni was also observed which provided high temper-
ature corrosion resistance to Superni 600. Table 4 sum-
marizes the performance of various alloys, in which the
.
.
Bal.
Bal.
Bal.
Bal.
Bal.
Bal.
“Performance” column shows comparison of alloys in
Ni
decreasing order of their corrosion resistance.
.
Table : Composition of substrates.
.
Application of coatings enhances the corrosion resis-
Bal.
Bal.
Bal.
.
Fe
tance of alloys which can be observed from Table 5. HVOF
thermal spraying technique of a coating with high chromium
ASTM-SA grade A steel
content has been preferred for substrates because of the good
adherence and high-density properties achieved by HVOF
Name of substrate
process. Also, chromium coating on reaction with salts forms
Superalloy C
Superfer
chromium oxide which plays a key role in improving the
Superni
Superni
Super H
Superni
Superni
corrosion resistance of the substrate. However, it has been
T alloy
HSS
N
observed that the type of biomass being burnt and thermal
IC
cycles taking place inside the biomass boiler also play a
398 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
Table : Corrosion resistance performance of various alloys based on literature.
Alloy name with coating Testing atmosphere Testing atmo- Corrosion performance Application of alloys
(if used) sphere
temperature
#Steel, TPH, Super- wt% KCl + wt% °C for cycle Superalloy C > TPH > #Steel Superheaters of
alloy C (Luo et al. ) KSO of h boilers
Superni , Superni , NaSO–%V °C Superni > Superni > Superfer H Superheater tubes,
Superfer H (Kamal turbine engines
et al. )
Superni , Superni Silicon carbide tube °C for Superni > Superni Boiler tubes, gas
(Gupta et al. ) furnace cycles turbines
N, N, N LiCl–LiO °C N > N > N Electrolytic reduction
(Cho et al. ) environment
NiAl based IC, IC wt% NaSO– wt °C IC > IC Superheater tubes,
(Zhao et al. ) % NaCl turbine engines
Superni , Superni , Thermal power plant °C for Superni > Superni > Superfer Superheater tubes of
Superfer , Superni (superheater zone) cycles > Superni thermal power plants
(Mishra et al. )
HSS (bare) and Actual husk fired boiler °C Coated HSS > uncoated HSS Economizers,
NiCr coated HSS reheater, superheater,
(Gada et al. ) air preheater
Superfer H, Superco NaSO–%V °C YO added Superni > YO added Steam boiler tubes,
, Superni with Superfer H > YO added Superco gas turbines
addition of YO (Singh
et al. )
H Steel, CrC–NiCr NaSO–Fe(SO) °C for Coated HSS > uncoated HSS Superheater tubes,
coated H steel (Kaur cycles steam turbines
et al. )
T Steel, CrC–NiCr NaSO–Fe(SO), °C Coated T > uncoated T boiler steel in all Boiler tubes, steam
coated T Steel (Kaur air, actual boiler there environments turbines
et al. ) environment
Carbon steel tube St ., Biomass fired boiler – °C Highest melting state in NiCrAl and Tubes at hot and cold
Ni–Cr–.Mo, Ni–Cr unmolten particles were observed in economizers of boilers
< Fe–Mo–Nb, Ni–Cr– NiCrMo and NiCrMo
Al–Y (Oksa et al. a)
T steel, CrO plasma %NaSO–%VO °C for Coated T > uncoated T Superheater tubes
sprayed T steel (Singh in silicon carbide tube cycles
et al. ) furnace
Superni , NiCrAlY coated NaSO + %VO °C Coated Superni > uncoated Superni Superheater tubes,
Superni (Rana et al. in silicon carbide tube gas turbines
) furnace
Ni–Al coated Superni , NaSO + %VO °C Coated Superfer > coated Superni Boiler tubes
Superni , Superfer > coated Superni
(Mahesh et al. b)
NiCrAl coated Superni , NaSO + %VO °C for Coated Superni > coated Superfer Hot corrosion boiler
Superni , Superfer cycles > coated Superni tubes and turbines
(Mahesh et al. a) components
primary role in the determination of the coating required. with high thermal cycles (Oksa et al. 2013; Wu et al. 2018).
Therefore, for the wood-fired plant with less number of Thus, the coating to be used depends on the material of the
thermal cycles, Ni and Ni2Al3 coatings are preferred, which boiler tube, number of thermal cycles, coating technique and
on the other hand, show poor behavior in fire straw plants type of biomass being burnt.
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 399
4 Corrosion-specific discussion because the deposition of fine powder at high velocity re-
sults in high bonding and mechanical strength of the coated
From the literature, it can be observed that the maximum metal surface (Kawahara 2016a; Zhou et al. 2016). Around
shutdown of biomass-fired boilers was due to the problem 47.95% of the literature accounted for the use of HVOF
of corrosion at high temperatures. The introduction of technique for the application of coatings. This is because
biomass boilers with high-temperature steam has resulted HVOF results in highly dense and well-adhered coatings
in the rise of high-temperature corrosion of superheater that can significantly reduce high-temperature corrosion
(Paul and Harvey 2013). HVOF employs the use of high
tubes. The concentrations of chlorine and potassium
coating particle velocity with low particle temperature
present in the biomass fuel being burnt can significantly
which results in dense coatings (Oksa et al. 2013). 23.29% of
increase the oxidation and corrosion of boiler tubes. The
the literature preferred the use of superalloys as superheater
presence of chlorine results in accelerated metal loss,
materials due to their advanced corrosion-resistant proper-
corrosion, the formation of voids and loosening of scales
ties. Superni 718, Superni 75 and Superfer 800H have been
(Mudgal et al. 2014b). The HCl gas that is often derived in
mostly used as material for superheater tubes. During
the form of flue gas does not possess high partial pressure
biomass combustion, Superni 75 results in the formation of
to cause severe high-temperature corrosion but the com-
scales containing NiO, Cr2O3 and NiCr2O4 that provide
bination of HCl gas with sulfides can enhance corrosion,
resistance against high-temperature corrosion. Superni 718
resulting in impingement of flame with poor combustion
and Superfer 800H also provided corrosion resistance due to
(Parthiban 2006). The presence of alkali chloride salts in
the formation of iron oxides and sulphides of Ni and Fe
deposits can accelerate corrosion by metal surfaces by
(Kamal et al. 2010). 8.22% literature accounted for detona-
combining with Sulphur dioxide gas, which results in tion gun (D-gun) sprayed coating because this process of
sulfation of deposits, liberating HCl gas close to the su- thermal coating results in the deposition of coating with fine
perheater tubes (Berlanga and Ruiz 2013; Frandsen 2005; grains with very low porosity (Kamal et al. 2008). Plasma
Nielsen et al. 2000). Therefore, research has been done spray was also used by 5.48% literature for coating the su-
and is still continuing to search for solutions that can peralloys with Ni–Al coating. This coating was preferred for
combat the high-temperature corrosion problem in applications requiring Ni–Al coating because of its ability to
biomass-fired boilers. With an increase in high- provide a coating with the porosity of 2.0–5.0% (Prakash et
temperature corrosion, the production losses have also al. 2005; Sidhu et al. 2006; Sidhu and Prakash 2003; Singh et
increased, resulting in ineffective biomass combustion al. 2007). Cold spray technique was used for the coating of
(Sharpconsultant 2011). Other biomass combustion Ni–Cr coatings on boiler steel, which accounted for 1.37% of
problems like fouling, agglomeration, emissions of heavy the literature. The formation of chromium oxide with
metals, low heating value and storage problems can be NiCr2O4 provided high oxidation resistance from chloride
easily solved with the help of low-cost solutions but high- and potassium salts (Bala et al. 2009). 13.7% literature used
temperature corrosion requires the use of coatings and chemical vapour deposition (CVD), electroless deposition,
superalloys, the usage of which is not so economical. So, cementation, electroplating, aluminizing, weld overlay,
researchers are continuously searching for cost-friendly laser cladding, and high velocity air fuel (HVAF) coating
solutions that can prevent the sudden shutdown of
biomass boilers.
In order to know more about the research that has
been done and is still continuing on high-temperature
corrosion, 73 research papers were considered to know
about the techniques that are being used to mitigate the
problem of high-temperature corrosion at 400–900 °C in
biomass boilers. Figure 3 discusses the techniques of
coatings and the usage of superalloys for reducing high-
temperature corrosion of superheater tubes. The application
of thermal spray coatings has proved to be more effective in
the deposition of highly dense and durable coatings over
metal surfaces (Bradshaw et al. 2013; Ruusuvuori et al. 2011;
Singh et al. 2012; Uusitalo et al. 2002). This led to the Figure 3: Techniques used to control high temperature corrosion
development of high velocity oxy fuel (HVOF) process resistance of biomass fired boiler tubes based on 73 publications.
400 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
It was observed that 27.78% of the literature used Ni–Cr
coating for improving the high-temperature corrosion resis-
tance of the boiler tube material. Ni and Cr combine to form
NiO and Cr2O3 in the oxide scale that acts as a barrier,
providing protection against high-temperature corrosion
(Kaushal et al. 2011, 2014; Meißner et al. 2020; Montero and
Galetz 2019). 12.96% of literature preferred the addition of
aluminium and yttrium to Ni-Cr coating. On the usage of
NiCrAl as coating, apart from NiO and Cr2O3, Al2O3 was also
formed which enhanced the corrosion resistance of the sub-
strate at high temperature. On addition of yttrium to NiCrAl
coating, Al3Y was also formed along with NiO, Cr2O3 and
Al2O3. With an increase in the number of cycles, the sub-
Figure 4: Various coating materials being used in anti-corrosive layers of Cr2O3 and Al2O3 in the oxide scale depleted and the
coatings based on 54 publications. dense layer of Al3Y was responsible for providing high-
temperature corrosion resistance (Mahesh et al. 2008a; Rana
techniques which also provided corrosion resistance to et al. 2014). Cr3C2–NiCr was accounted by 25.93% literature
boiler tubes at high temperature (Liu et al. 2014; Sadeghi- for improvement in corrosion resistance of the superheater
meresht et al. 2017, 2018). Weld overlay is not a mature tubes. During biomass combustion, Cr3C2–NiCr coating led
technology for biomass boilers as research needs to be done to the formation of protective oxides like NiCr2O4 and Cr2O3,
in this field for improvement of cost and adequate selection which were responsible for improving the corrosion resis-
of material, which will help in improving durability in future tance of the superheater material at high temperature (Kaur
(Kawahara 2016a). et al. 2012; Mudgal et al. 2014c,d). Ni–Al coating was used in
The various proportions of coating materials that are 16.67% literature because due to the formation of chromium
being used for making coatings with high-temperature band close to the coating substrate, the high-temperature
corrosion resistance were also investigated based on 54 corrosion resistance was enhanced for Superfer 800 super-
works of literature. Figure 4 depicts the various coating ma- alloy. Ni–Al acts as a protective coating for boiler tubes due
terials being used for the formation of anti-corrosive coatings. to the formation of protective NiAl2O4 spinels that provide
Table : Hot corrosion resistance of coated alloys.
Base alloy Coating used Performance of base and coated alloys XRD analysis
Superni ( NiCrAlY coating by Coated Superni performed better than uncoated After cycles, peaks of CrO, AlO and
cycles) (Rana et al. HVOF technique superalloy. Weight change became constant after AlY were obtained. After cycles, peaks of
) cycles due to corrosion resistance offered by AlO and AlY intensified for corrosion
coating. resistance.
HSS (Gada NiCr coating by Coated HSS performed better as average For coated steel, peaks of NiCrO, KCrO,
et al. ) HVOF technique thickness loss for bare steel = . mm and for MgSiO, FeO and NiSO were obtained.
coated steel = . mm. Ni and Cr oxides were protective against
corrosion.
SAE H Steel CrC-NiCr coating by Coated steel performed better as cumulative weight Peaks were obtained for CrO and CrC.
( cycles) (Kaur HVOF technique loss/area for coated steel = . mg/cm and for Rich chromium oxide protected the metal
et al. ) uncoated steel = . mg/cm. against corrosion.
Superni CrC–NiCr coating Coated Superni performed better as weight CrO, CrC and NiCrO peaks were ob-
(Kumar et al. by detonation gun change/area changed from . to . mg/cm on tained that provided corrosion resistance to
) technique application of coating. Superni .
T Steel ( cy- CrO coating by Coated steel performed better as weight gain/area For uncoated steel, peak was obtained for
cles) (Singh et al. plasma spray for coated steel = . mg/cm and for uncoated FeO and for coated steel, peak was ob-
) technique steel = . mg/cm. tained for CrO that provided corrosion
resistance.
ASTM SA T CrC–NiCr coating Coated steel performed better as thickness of metal FeO and CrO peaks were obtained for
boiler steel (Kaur by HVOF technique loss for coated steel was . mm and that for un- uncoated steel. CrNi, CrNi, NiCrO, CrO
et al. ) coated steel was . mm. and CrC peaks were obtained for coated
steel.
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 401
Table : Corrosion resistance mechanism of alloys based on literature.
Alloy with coating name and Boiler environment Oxides formed Comments
method
T steel, Ni–Cr coating by NaSO–%VO ( °C) and NiO, CrO, NiCrO, 1) HVOF showed no spallation of oxides.
HVOF and D-gun technique (Kau- superheater of thermal power FeO 2) Fe2O3 with Al2O3 and SiO2 were respon-
shal et al. ) plant ( °C) sible for corrosion.
3) Layer of NiO and Cr2O3 in oxide scale
provided corrosion resistance.
T steel, NiCr coating by HVOF, Paste of NaSO–%VO was CrO, NiCrO, FeO, 1) D-gun spray technique was best.
D-gun and Cold spray techniques applied and then placed in sili- NiO, NaVO 2) NaVO3 and Fe2O3 acted as oxygen carriers,
(Kaushal et al. ) con carbide tube furnace leading to corrosion of base metals.
( °C) 3) Cr2O3, NiCr2O4 oxide layer provided
corrosion resistance.
Superni , Superni , Superfer NaSO–%VO ( °C) CrO, FeO, AlO, 1) Superni 750 performed the best.
, NiCrAl coating by HVOF NaVO, NiO, SiO, MnO, 2) NaVO3 and Fe2O3 acted as corrosive spe-
technique (Mahesh et al. a) VO cies for superalloys.
3) Oxide scale layer rich in Cr2O3 and Al2O3
and subscale regions containing nickel
rich splats provided corrosion resistance.
Superni , NiCrAlY coating by NaSO–%VO ( °C) AlY, AlO, CrO, 1) YVO4 and Cr depleted layer acted as cor-
HVOF technique (Rana et al. ) NiVO, YVO rosive species.
2) Under Cr depleted layer, Al oxidized to
form sublayer of Al2O3 along with Al3Y,
which provided corrosion resistance.
T steel, CrC–NiCr NaSO–Fe(SO) in silicon FeO, AlO, SiO, CrNi, 1) Fe2O3, Al2O3 and SiO2 acted as corrosive
coating by HVOF technique (Kaur carbide tube ( °C) CrC, CrO, FeS, species.
et al. ) NiCrO 2) Oxide scales consisting of NiCr2O4 and
Cr2O3 provided corrosion resistance.
Superfer , Superni , Superni NaSO–%VO in silicon NiO, NiAlO, NiCrO, 1) For uncoated superlloys, Fe2O3 and V2O5
, Ni–Al coating by HVOF tech- carbide tube furnace ( °C) MnO, CrO, FeO resulted in corrosion.
nique (Mahesh et al. b) 2) Al2O3, NiO and Cr2O3 provided corrosion
resistance to coated superalloys.
3) Superfer 800 performed the best due to
the formation of NiAl2O4 spinels under
sublayer of Al and Cr.
Stainless steel, Inconel KCl salt deposits ( °C) KCrO, CrO, NiO 1) Inconel 625 coating could not perform well
coating by cold spray, HVAF, HVOF and chlorine was able to penetrate coated
and arc spray techniques (Fan- specimens.
tozzi et al. ) 2) K2CrO4 was also responsible for sample
damage.
3) HVOF and arc spray methods resulted in
reduced porosity.
T Steel, FeCrAl coating by HVOF Coal biomass co-fired boiler FeO, chromium and 1) Sulphur was responsible for corrosion of
technique (Hussain et al. ) (– °C) aluminium rich oxides samples.
2) Mixed outer oxide of Al and mixed inner
oxide of Cr provided corrosion resistance.
Cr oxides containing Al rich phases were
present in inter splat oxides that also
provided corrosion resistance.
SS, FeCrB coating by HVOF Fireside corrosion test, with and MnWO, FeO, FeO, 1) Sample loss was observed in laser clad-
and laser cladding techniques without KCl deposits ( °C) CrO in the absence of ding without deposits and Cr2O3 provided
(Bai et al. ) deposits. protection against corrosion.
MnCl, FeO, FeO in 2) In the presence of deposits, corrosion
the presence of deposits. resistance could not be provided and
chlorine was found underneath the oxides
that resulted in severe corrosion of metal.
402 S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers
Table : (continued)
Alloy with coating name and Boiler environment Oxides formed Comments
method
Inconel , CrC–WC–NiC- NaCl–KCl–NaSO ( °C) FeO, NiCrO, NiO, 1) Chloride salts and Fe2O3 were responsible
oCrMo and CrC–(NiCr) coat- CrO for CrC–NiCr for degradation of substrate.
ings by HVOF technique (Zhou coating. 2) Cr3C2–WC–NiCoCrMo performed better
et al. ) CrO, NiO,MoO, CoO, and corrosion resistance was increased
WO, NiCrO for CrC– due to the formation of W, Co, Mo and Cr
WC–NiCoCrMo coating oxides.
resistance against high-temperature corrosion (Mahesh et al. during its growing stage. On the other hand, burning the
2008b; Wu et al. 2017, 2019). 3.7% literature used Ni based same amount of fossil fuels results in the release of large
Inconel 625 coating for protection of metal surfaces against quantities of carbon dioxide in a short period. Thus, biomass
high-temperature corrosion. However, this coating failed to is a potential resource that can be used in boilers to
provide corrosion resistance above 750 °C and chlorine were completely replace fossil fuels, saving the environment from
found to penetrate boiler tubes inspite of the application of harmful fossil emissions. From the literatures, it has been
Inconel 625 coating (Fantozzi et al. 2016; Kaushal et al. 2014). found that biomass is highly volatile and reactive fuel with
Fe–Cr coatings have been used in 9.26% literature and it has very low carbon content. It is an eco-friendly and renewable
been found that Ni–Cr coatings show better high- fuel with reduced nitrogen and Sulphur content. Also, if
temperature corrosion resistance than Fe–Cr coatings. Ni biomass is co-fired with coal, 93% reduction in carbon di-
has proved to be more corrosion resistant than Fe (Oksa et al. oxide has been reported, in comparison to the combustion of
2015b). Other elements like boron, tungsten and aluminium hard coal. Agricultural waste can be properly utilized as
are often added to Fe–Cr coating to enhance the corrosion biomass which reduces our dependence on fossil fuels. For
resistance properties of Fe–Cr (Oksa et al. 2014b). The addi- storage and transportation of biomass, labor will be
tion of aluminium resulted in the formation of aluminium required, thus, generating employment opportunities.
rich mixed oxide on the outer layer and chromium-rich Burning of biomass in boilers often results in ash-
mixed oxide on the inner layer of the substrate-coating related problems like fouling, agglomeration, emission of
interface. Boron addition to Fe–Cr resulted in the formation trace metals, gaseous emissions (CO, NOx, N2O and SOx), low
of protective CrB2 which provided resistance against corro- heating value, storage and transportation problems and
sion at high temperature (Hussain et al. 2015; Reddy et al. corrosion at high temperature.
2017). 3.7% of other coatings include silicon aluminide and These problems can be easily tackled by using the
Cr3C2–WC–NiCoCrMo coatings which have also helped in following countermeasures:
improving high-temperature corrosion resistance of sub- Fouling can be reduced by the addition of a composite
strate materials. Cr3C2–WC–NiCoCrMo is said to perform additive to lower the content of potassium in the biofuel.
better than Cr3C2–NiCr coating because of the presence of The reduction of chloride by the addition of ammonium
elements like tungsten, cobalt, molybdenum and chromium sulfate is also an effective countermeasure. Leaching and
have certainly proved to reduce the corrosion rate of boiler optimization of process parameters like airflow rate and
tubes (Zhou et al. 2017). The corrosion resistance mecha- deposition probe temperature have also been effective in
nisms for various alloys discussed in the literature have been reducing fouling.
summarized in Table 6. Olivine bed material has resulted in reduced agglom-
eration. Change in reactor design and the use of additives
like kaolin and ammonium sulfate have reduced agglom-
5 Summary and conclusions eration. Lower bed temperature, higher fluidization velocity
and finer bed particles have proved to be ideal operating
Biomass exhibits carbon-neutral behavior in the environ- parameters for the reduction in agglomeration.
ment. It absorbs solar energy and carbon dioxide in its Heavy metals like lead and cadmium can be adsorbed
growing stage. When it is burnt in oxygen, it gives out car- by silicates and aluminosilicates. Activated carbon, post-
bon dioxide and when fully burnt, it is believed to give out precipitation method and ion-exchange method have been
the same amount of carbon dioxide that it had absorbed very effective in the reduction of heavy metal emissions.
S. Sharma et al.: Adoption of strategies for clean combustion of biomass in boilers 403
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The low heating value of biomass fuel results in igni-
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Bionotes
Deepa Mudgal
Shrutika Sharma Department of Mechanical Engineering,
Department of Mechanical Engineering, Thapar Institute of Engineering and
Thapar Institute of Engineering and Technology, Patiala, Punjab 147004, India
Technology, Patiala, Punjab 147004, India deepa.mudgal@thapar.edu
shrutikasharma2009@gmail.com
Deepa Mudgal has worked as an assistant professor in Department
of Mechanical Engineering, Thapar Institute of Engineering and
Technology Patiala, Punjab since 2016. She has completed her PhD
at Indian Institute of Technology Roorkee in 2015. Her areas of
Shrutika Sharma is currently pursuing MTech in Department of
research are thermal spray coating, and high temperature
Mechanical Engineering, Thapar Institute of Engineering and
corrosion and erosion. She has published 21 research papers in
Technology Patiala, India. She obtained her BTech from SRM Institute
different SCI/non SCI/Scopus indexed journals. She has also co-
of Science and Technology (Department of Mechanical Engineering)
authored a book chapter on design, development and application
Chennai, India in 2019. Her areas of interest are tribology, non-
of nanocoatings.
conventional sources of energy, corrosion studies, and additive
manufacturing processes.
Hiralal Bhowmick
Department of Mechanical Engineering,
Mayank Sharma
Thapar Institute of Engineering and
Department of Mechanical Engineering,
Technology, Patiala, Punjab 147004, India
Thapar Institute of Engineering and
hiralal.bhowmick@thapar.edu
Technology, Patiala, Punjab 147004, India
mayank.sharma1296@gmail.com
Hiralal Bhowmick has completed his PhD at IISc Bangalore, India in
2013 and is currently working as an associate professor in Thapar
Institute of Engineering & Technology, India. He has published 24
Mayank Sharma is pursuing MTech in Department of Mechanical SCI/SCIE papers and supervised 2 PhD and 11 Master’s theses. He is
Engineering, Thapar Institute of Engineering and Technology Patiala, a recognized reviewer of some of the highly reputed journals
India. He obtained his BTech from SRM University (Department of published in the field. His research areas include tribology,
Mechanical Engineering), Chennai, India in 2018. His areas of interest are nanolubricants, composites, study of mechanical behaviour of
IC engines, corrosion studies, production planning, additive materials.
manufacturing. He is skilled in softwares like UG-NX, Mimics, AutoCad and
ProE/Creo.
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